Functionalized olefin polymers, compositions and articles prepared therefrom, and methods for making the same

ABSTRACT

In one aspect the invention provides a melt process for preparing a functionalized olefin multiblock interpolymer, said process comprising grafting onto the backbone of the olefin multiblock interpolymer at least one compound comprising at least one “amine-reactive” group to form a grafted olefin multiblock interpolymer, and reacting a primary-secondary diamine or an alkanolamine with the grafted olefin multiblock interpolymer, without the isolation of the grated olefin multiblock interpolymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This present application is a divisional application of the U.S.application Ser. No. 12/519,504, filed on Jun. 16, 2009, now U.S. Pat.No. 8,450,430, which is a 371 application of International ApplicationNo. PCT/US2007/088599, filed on Dec. 21, 2007, which claims the benefitof U.S. Provisional Application Nos. 60/876,287 filed on Dec. 21, 2006,60/952,272 filed on Jul. 27, 2007, 60/952,425 filed on Jul. 27, 2007,60/955,464 filed on Aug. 13, 2007 and 60/952,271 filed on Jul. 27, 2007.

FIELD OF INVENTION

The invention provides olefin multiblock interpolymers comprising aminefunctionality and/or hydroxyl functionality, and methods for making thesame. The invention also provides articles comprising at least onecomponent prepared from such compositions.

BACKGROUND OF THE INVENTION

Polyolefins, as a class of materials, have relatively poor adhesion andcompatibility with more polar polymeric materials. In most cases, aseparate adhesive is required in order to adhere polyolefins to polarsubstrates like polyesters, polyamides, polyurethanes, and the like.Similarly, a third component compatibilizer typically has to be used toprepare satisfactory melt blends of polyolefins with other more polarthermoplastics.

Typically, anhydride grafting onto polyolefins is used to provide somelevel of compatibility and/or adhesion to more polar substrates,however, this functionality is not optimum for adhesion in many cases.In particular, strong adhesion to polyurethane (PU) substrates isachieved if covalent bonds can be formed across the interface of apolyolefin-polyurethane structure. Adhesion to PU substrates can beimproved using a polyolefin with functional groups that can react withurethane linkages and/or terminal isocyanate groups. Attempts have beenmade to incorporate amine functionality and/or hydroxyl functionalityinto a polyolefin, by reacting primary diamines or alkanolamines withanhydride grafted polyolefins. However, it has been difficult to preparesuch functional polymers, since the unreacted amine groups and unreactedhydroxyl groups of the imide can further react with anhydride to formbranched and crosslinked structures in the final polymer product. Inaddition, such reactions typically required the initial formation andisolation of an anhydride grafted polyolefin, prior to the reaction withthe functionalization agent (diamine or alkanolamine). Thus the separateformation and isolation of the graft precursor adds additionalprocessing costs to the functionalization reaction.

U.S. Pat. No. 5,424,367 and U.S. Pat. No. 5,552,096 and U.S. Pat. No.5,651,927 disclose sequential reactions in one extruder for thefunctionalization of a polymer. Each reaction zone has means forintroduction of reagents, for mixing of reagents with polymer and forremoval of by/co-products or unreacted reagents. These patents do notdisclose the use of primary-secondary diamines to reduce competingcrosslinking reactions.

International Publication No. WO 93/02113 discloses (1) graft polymerscomprising reactive amine functionality that are prepared by reacting athermoplastic polymer, comprising at least one electrophilicfunctionality sufficient to react with primary amino groups, and (2) acompound comprising a primary amine and a secondary amine, the secondaryamine having reactivity approximately equal to, or less than, theprimary amine. However, this reference does not disclose a subsequentin-situ functionalization of a grafted polyolefin, without the priorisolation of the grafted polyolefin.

Additional functionalization reactions are disclosed in U.S. Pat. No.6,469,099 B1; U.S. Pat. No. 5,599,881; U.S. Pat. No. 5,886,194; U.S.Pat. No. 4,137,185; U.S. Pat. No. 4,374,956; U.S. Pat. No. 3,471,460;U.S. Pat. No. 3,862,265; U.S. Publication No. US 20060025316; EuropeanApplication No. 0 634 424 A1; European Application No. 0 036 949 A;International Publication No. WO 01/29095; International Publication No.WO 06/039774; and in the following references, “Melt Amination ofPolypropylenes,” Q. W. Lu et al., Journal of Polym. Sci.-Polym. Chem.,43, 4217 (2005); “Reactivity of Common Functional Groups withUrethanes,” Q. W. Lu et al., Journal of Polym. Sci.-Polym. Chem., 40,2310 (2002); and “Melt Grafting of Maleamic Acid onto LLDPE,” A. E.Ciolino et al., Journal of Polym. Sci.-Polym. Chem., 40, 3950 (2002).

However, these references do not disclose amine functionalized andhydroxyl functionalized polyolefins that can be prepared in a low costmanner, without producing significant amounts of branching andcrosslinks in the final polymer product. There is a need for an in-situpreparation of amine functionalized or hydroxyl functionalizedpolyolefin that does not require the initial formation and isolation ofa graft polyolefin precursor, and that does not result in the formationof significant branching and crosslinking in the functionalizedpolyolefin. Moreover, there is a need for an amine-functionalizedpolyolefin that provides enhanced compatibility and/or adhesion topolyurethane substrates. These needs and others have been met by thefollowing invention.

SUMMARY OF THE INVENTION

In one aspect, the invention provides a process for preparing afunctionalized olefin multiblock interpolymer, said process comprisingthe following steps:

-   -   grafting onto the backbone of an olefin multiblock interpolymer        at least one compound comprising at least one “amine-reactive”        group to form a grafted olefin multiblock interpolymer;    -   reacting a primary-secondary diamine with the grafted olefin        multiblock interpolymer; and    -   wherein step B) takes place subsequent to step A), without the        isolation of the grafted olefin multiblock interpolymer, and        wherein both steps A) and B) take place in a melt reaction.

In another aspect, the invention provides a process for preparing afunctionalized olefin multiblock interpolymer, said process comprisingthe following steps:

-   -   grafting onto the backbone of an olefin multiblock interpolymer        at least one compound comprising at least one “amine-reactive”        group to form a grafted olefin multiblock interpolymer;    -   reacting a alkanolamine with the grafted olefin multiblock        interpolymer; and    -   wherein step B) takes place subsequent to step A), without the        isolation of the grafted olefin multiblock interpolymer, and        wherein both steps A) and B) take place in a melt reaction.

In another aspect, the invention provides a process for preparing afunctionalized olefin multiblock interpolymer, said process comprisingthe following steps:

-   -   A) grafting onto the backbone of an olefin multiblock        interpolymer at least one compound comprising at least one        “amine-reactive” group to form a grafted olefin multiblock        interpolymer;    -   B) reacting a primary-secondary diamine or an alkanolamine with        the grafted olefin multiblock interpolymer; and    -   C) wherein step B) takes place subsequent to step A), without        the isolation of the grafted olefin multiblock interpolymer, and        wherein both steps A) and B) take place in a melt reaction. In a        preferred embodiments, the primary-secondary diamine is selected        from N-ethylethylenediamine, N-phenylethylenediamine,        N-phenyl-1,2-phenylene-diamine, N-phenyl-1,4-phenylenediamine,        or 4-(aminomethyl)piperidine. In a preferred embodiment, the        alkanolamine is selected from 2-aminoethanol,        2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol,        2-(2-aminoethoxy)-ethanol or 2-aminobenzyl alcohol.

In one embodiment, both steps A and B take place in a batch reactor.

In another embodiment, both steps A and B take place in a Brabendermixer, a Busch mixer or a Farrel mixer.

In another embodiment, step A takes place in an extruder, and step Btakes place in a gear pump.

In another embodiment, step A takes place in an extruder, and step Btakes place in a batch mixer. In a further embodiment, the batch mixeris of commercial dimensions. In another embodiment, the batch mixer isof lab scale or pilot plant dimensions.

In another embodiment, step A takes place in an extruder, and step Btakes place in a separate extruder.

In another embodiment, there is no purification step between steps A andB.

In another embodiment, there is no venting of volatiles between steps Aand B.

In another aspect, the invention provides a process for preparing animide functionalized olefin multiblock interpolymer, said processcomprising the following steps:

-   -   grafting onto the backbone of an olefin multiblock interpolymer,        in a melt reaction, at least one compound of the following        formula (IV) to form a grafted olefin multiblock interpolymer.

-   -   and thermally treating the grafted olefin multiblock        interpolymer to form the imide functionalized olefin multiblock        interpolymer,        and wherein R1 and R2 are, independently, either hydrogen or a        C1-C20 hydrocarbyl radical, which is linear or branched; R3 is        hydrogen or a C1-C20 hydrocarbyl radical, which is linear or        branched; R4 is a hydrocarbyl di-radical, which is linear or        branched; X is OH or NHR₅, where R5 is a hydrocarbyl radical,        which is linear or branched, or a hydroxyethyl group.

In yet another aspect, the invention provides a process for preparing aimide functionalized olefin multiblock interpolymer, said processcomprising the following steps:

-   -   A) functionalizing the olefin multiblock interpolymer with at        least one compound comprising at least one “amine-reactive”        group to form a grafted olefin multiblock interpolymer;    -   B) blending the grafted olefin multiblock interpolymer, in a        solid, non-molten form, with at least one primary-secondary        diamine;    -   C) imbibing the primary-secondary diamine into the grafted        olefin multiblock interpolymer;    -   D) reacting the primary-secondary diamine with the grafted        olefin multiblock interpolymer to form an imide functionalized        olefin multiblock interpolymer.

The olefin multiblock interpolymer employed in the aforementionedprocesses often comprises an ethylene/α-olefin multiblock interpolymer,wherein the ethylene/α-olefin multiblock interpolymer has one or more ofthe following characteristics:

(1) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or

(2) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1; or

(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)²; or

(4) an Mw/Mn from about 1.7 to about 3.5, and is characterized by a heatof fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsiusdefined as the temperature difference between the tallest DSC peak andthe tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH havethe following relationships:

ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,

ΔT≧48° C. for ΔH greater than 130 J/g.

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30 C.; or

(5) an elastic recovery, Re, in percent at 300 percent strain and 1cycle measured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase: Re>1491−1629(d); or

(6) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene inter polymer fraction eluting between the sametemperatures, wherein said comparable random ethylene inter polymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(7) a storage modulus at 25° C. G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isin the range of about 1:1 to about 9:1.

The olefin multiblock interpolymer characteristics (1) through (7) aboveare given with respect to the interpolymer before any significantcrosslinking or functionalization, i.e., before crosslinking orfunctionalization. The multiblock interpolymers useful in the presentinvention may or may not be initially crosslinked or functionalizeddepending upon the desired properties. By using characteristics (1)through (7) as measured before crosslinking or functionalizing is notmeant to suggest that the interpolymer is required or not required to becrosslinked or functionalized—only that the characteristic is measuredwith respect to the interpolymer without significant crosslinking orfunctionalization. Crosslinking and/or functionalization may or may notchange each of these properties depending upon the specific polymer anddegree of crosslinking or functionalization.

DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship forethylene/α-olefin interpolymers (represented by diamonds) as compared totraditional random copolymers (represented by circles) and Ziegler-Nattacopolymers (represented by triangles).

FIG. 2 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene polymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer examples 10-19. The “X” symbols represent polymer examplesA*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from ethylene/α-olefin interpolymers (represented by thesquares and circles) and traditional copolymers (represented by thetriangles which are various Dow AFFINITY® polymers). The squaresrepresent ethylene/butene interpolymers; and the circles representethylene/octene interpolymers.

FIG. 4 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (represented by the circles)and comparative polymers E and F (represented by the “X” symbols). Thediamonds represent traditional random ethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (curve 1) and for comparativeF (curve 2). The squares represent Example F*; and the trianglesrepresent Example 5.

FIG. 6 is a graph of the log of storage modulus as a function oftemperature for comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene-copolymer (curve 3) and for two ethylene/1-octeneblock copolymers made with differing quantities of chain shuttling agent(curves 1).

FIG. 7 shows a plot of TMA (1 mm) versus flex modulus for some polymers(represented by the diamonds), as compared to some known polymers. Thetriangles represent various Dow VERSIFY® polymers; the circles representvarious random ethylene/styrene copolymers; and the squares representvarious Dow AFFINITY® polymers.

FIG. 8 depicts electron micrographs showing particle sizes and shapes ofseveral polyethylene/polyurethane blends.

FIG. 9 depicts electron micrographs showing particles sizes and shapesof several amine-functionalized polyethylene/polyurethane blends and twocontrols.

FIG. 10 is a schematic a peel test specimen.

FIG. 11 is a schematic of a peel test set-up.

FIG. 12 represents a peel strength profile of aMAH-Engage™/Polycarbonate.

FIG. 13 represents a peel strength of profile of a primary hydroxylfunctionalized Engage™/Polycarbonate.

FIG. 14 represents a peel strength profile of secondaryamine-functionalized Engage™/Polycarbonate.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to the preparation of amine and/or hydroxylfunctionalized polyolefins, using an in-situ melt reaction. In oneaspect of the invention, the preparation of the functionalizedpolyolefin takes place in a batch reactor. In another aspect, thepreparation takes place in a reactive extrusion process.

The functionalized polyolefins prepared therein have utility inapplications where improved compatibility and/or adhesion to polarpolymers, such as polyurethane, polyester, polyvinylchloride,polyamides, polyacrylates, polyacrylonitrile, cellulosics, and the like.The inventive polyolefins find particular use in shoe soles, automotiveinstrument panel skins, blends with thermoplastic polyurethanes, and thelike. This invention also provides various in-situ melt processes thatcan be used to prepare said functionalized polyolefins, avoiding theneed to prepare and isolate an anhydride grafted polyolefin precursor.

The functionalized polyolefins may also be used as tie layers betweenextruded sheets, films or profiles, for fibers or dispersions, inautomotive skins, awnings, tarps, roofing construction (for example,adhesives to epoxy, urethane or acrylic-based substrates for all roofingapplications, such as insulation bonding, liquid roofing, façadesealant, expansion joints, wet-room sealants, pitched roof,acrylics-adhered roof, bitumen bonding, and PUR-adhered refurbishment),paintable automotive skins and steering wheels, paintable injectionmolded toys, powder coatings, powder slush moldings or rotational castmoldings, consumer durables, grips, computer components, belts,adhesives, fabrics, carpets, artificial turf, coatings, wire and cable,raincoats and similar protective apparel. Additional applications aredescribed herein.

The invention provides a process for preparing a functionalized olefinmultiblock interpolymer, said process comprising the following steps:

-   -   grafting onto the backbone of an olefin multiblock interpolymer        at least one compound comprising at least one “amine-reactive”        group to form a grafted olefin multiblock interpolymer;    -   reacting a primary-secondary diamine with the grafted olefin        multiblock interpolymer; and    -   wherein step B) takes place subsequent to step A), without the        isolation of the grafted olefin multiblock interpolymer, and        wherein both steps A) and B) take place in a melt reaction.

In a preferred embodiment, the primary-secondary diamine is selectedfrom N-methyl-ethylenediamine, N-ethylethylenediamine,N-phenylethylenediamine, N-methyl-1,3-propanediamine,N-phenyl-1,2-phenylene-diamine, N-phenyl-1,4-phenylenediamine, or4-(aminomethyl)piperidine.

In another embodiment, the invention provides a process for preparing afunctionalized olefin multiblock interpolymer, said process comprisingthe following steps:

-   -   grafting onto the backbone of an olefin multiblock inter polymer        at least one compound comprising at least one “amine-reactive”        group to form a grafted olefin multiblock interpolymer;    -   reacting a alkanolamine with the grafted olefin multiblock        interpolymer; and    -   wherein step B) takes place subsequent to step A), without the        isolation of the grafted olefin multiblock interpolymer, and        wherein both steps A) and B) take place in a melt reaction.

In a preferred embodiment, the alkanolamine is selected fromethanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol,or 2-aminobenzyl alcohol.

In another aspect, the invention provides a process for preparing afunctionalized olefin multiblock interpolymer, said process comprisingthe following steps:

-   -   grafting onto the backbone of an olefin multiblock interpolymer        at least one compound comprising at least one “amine-reactive”        group to form a grafted olefin multiblock interpolymer;    -   reacting a primary-secondary diamine or an alkanolamine with the        grafted olefin multiblock interpolymer; and    -   wherein step B) takes place subsequent to step A), without the        isolation of the grafted olefin multiblock interpolymer, and        wherein both steps A) and B) take place in a melt reaction.

In a preferred embodiment, the primary-secondary diamine is selectedfrom N-methyl-ethylenediamine, N-ethylethylenediamine,N-phenylethylenediamine, N-methyl-1,3-propanediamine,N-phenyl-1,2-phenylene-diamine, N-phenyl-1,4-phenylenediamine, or4-(aminomethyl)piperidine.

In a preferred embodiment, the alkanolamine is selected fromethanolamine, 2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol,or 2-aminobenzyl alcohol.

In another embodiment, the invention provides a process for preparing animide functionalized olefin multiblock interpolymer, said processcomprising the following steps:

-   -   grafting onto the backbone of an olefin multiblock interpolymer,        in a melt reaction, at least one compound of the following        formula (IV) to form a grafted olefin multiblock interpolymer:

-   -   and thermally treating the grafted olefin multiblock        interpolymer to form the imide functionalized olefin multiblock        interpolymer.        and wherein R1 and R2 are, independently, either hydrogen or a        C1-C20 hydrocarbyl radical, which is linear or branched; R3 is a        hydrogen or a C1-C20 hydrocarbyl radical, which is linear or        branched: R4 is a hydrocarbyl di-radical, which is linear or        branched; X is OH or NHR₅, where R5 is a hydrocarbyl radical,        which is linear or branched, or a hydroxyethyl group.

In another embodiment, the invention provides a process for preparing animide functionalized olefin multiblock interpolymer, said processcomprising the following steps:

-   -   A) functionalizing the olefin multiblock interpolymer with at        least one compound comprising at least one “amine-reactive”        group to form a grafted olefin multiblock interpolymer;    -   B) blending the grafted olefin multiblock interpolymer, in a        solid, non-molten form, with at least one primary-secondary        diamine;    -   C) imbibing the primary-secondary diamine into the grafted        olefin multiblock interpolymer;    -   D) reacting the primary-secondary diamine with the grafted        olefin multiblock interpolymer to form an imide functionalized        olefin multiblock interpolymer.

In a further embodiment, the imbibing step takes place at roomtemperature. In another embodiment, the blending step takes place atroom temperature.

The olefin multiblock interpolymer in the aforementioned processescomprises an ethylene/α-olefin interpolymer, wherein theethylene/α-olefin interpolymer has one or more of the followingcharacteristics:

(1) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or

(2) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1; or

(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)²; or

(4) an Mw/Mn from about 1.7 to about 3.5, and is characterized by a heatof fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsiusdefined as the temperature difference between the tallest DSC peak andthe tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH havethe following relationships:

ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,

ΔT≧48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(5) an elastic recovery, Re, in percent at 300 percent strain and 1cycle measured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d); or

(6) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene interpolymer fraction eluting between the sametemperatures, wherein said comparable random ethylene interpolymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isin the range of about 1:1 to about 9:1.

The olefin multiblock interpolymer may be mixed or blended with one ormore additional polymers. One such additional polymer is anotherethylene-based polymer. In a further embodiment, the ethylene-basepolymer is an second ethylene/α-olefin interpolymer, and wherein theα-olefin is a C3-C20 α-olefin. In yet a further embodiment, the α-olefinis selected from 1-propene, 1-butene, 1-hexene, and 1-octene, andmixtures thereof.

Another polymer that that the olefin multiblock interpolymer may bemixed or blended with is a propylene-based polymer. In a furtherembodiment, the propylene-base polymer is a propylene/ethyleneinterpolymer or a propylene/α-olefin interpolymer, and wherein theα-olefin is a C4-C20 α-olefin. In yet a further embodiment, the α-olefinis selected from 1-butene, 1-hexene or 1-octene.

The invention also provides a composition comprising the functionalizedolefin multiblock interpolymer as described herein. In a furtherembodiment, the functionalized olefin multiblock interpolymer is presentin an amount greater than 50 weight percent, based on the total weightof the composition.

The invention also provides a composition comprising a functionalizedolefin multiblock interpolymer as described herein, and wherein thefunctionalized olefin multiblock interpolymer is present in an amountless than, or equal to, 20 weight percent, based on the total weight ofthe composition.

In another embodiment, the composition further comprising a polarpolymer selected from polyesters, polyamides, polyethers,polyetherimides, polyvinylalcohols or polyvinylchlorides. In anotherembodiment, the functionalized olefin multiblock interpolymer isdispersed in the polar polymer to form particles thereof, and whereinthe particles have a mean size less than, or equal to, 0.40 μm,preferably less than, or equal to 0.30 μm, and more preferably lessthan, or equal to, 0.20 μm.

The inventive methods and/or compositions may comprise a combination oftwo or more embodiments as described herein.

The invention also provides an over-molded article, the article formedfrom a polar substrate, and a molded overlay comprising an inventivecomposition. In another embodiment the polar substrate is formed from acomposition comprising a polycarbonate, and in a further embodiment, thepolar substrate has a textured surface at the interface of the substrateand the molded overlay

The invention also provides a laminated structure comprising a firstlayer and a second layer, and wherein the first layer is formed from aninventive composition, and the second layer is formed from a compositioncomprising a polar material. In a further embodiment, one of the layersis in the form of a foam. In another embodiment one of the layers is inthe form of a fabric. In another embodiment, laminated structure is inthe form of an awning, tarp or automobile skin or steering wheel. Inanother embodiment, wherein the second layer is formed from acomposition comprising a polycarbonate, and in a further embodiment, thesecond layer has a textured surface at the interface of the second layerand first layer.

The invention also provides a molded article comprising a firstcomponent and a second component, and wherein the first component isformed from a polar material, and the second component formed from aninventive composition. In a further embodiment, the article is in theform of an automobile skin, appliqué, footwear, conveyor belt, timingbelt or consumer durable.

The invention also provides an article comprising at least one componentformed from an inventive composition. In a further embodiment, thearticle is a carpet, an adhesive, a wire sheath, a cable, a protectiveapparel, a coating or a foam laminate. In another embodiment, thearticle is a tie layer between extruded sheets, films or profiles; a tielayer between cast sheets, films or profiles; an automotive skin; anawning; a tarp; a roofing construction article; a steering wheel; apowder coating; a powder slush molding; a consumer durable; a grip; ahandle; a computer component; a belt; an appliqué, a footwear component,a conveyor or timing belt, or a fabric.

The inventive articles and laminated structures may comprise acombination of two or more embodiments as described herein.

I. In-Situ Functionalization Reactions Using a Grafted Olefin MultiblockInterpolymer

a) Grafting Reactions

The olefin multiblock interpolymers disclosed herein may be modified bytypical grafting, hydrogenation, nitrene insertion, epoxidation, orother modification reactions, well known to those skilled in the art.Preferred modifications are grating reactions using a free radicalmechanism, and more preferably, grafting reactions that result in theformation of “amine-reactive groups” and “hydroxyl-reactive groups.”Such groups include, but are not limited to, anhydride groups, estergroups and carboxylic acid groups, and preferably the reactive group isan anhydride group.

Examples of reactive compounds that can be grafted onto the polymerichydrocarbon backbone include ethylenically unsaturated carboxylic acidssuch as maleic acid, fumaric acid, itaconic acid, acrylic acid,methacrylic acid, and crotonic acid; acid anhydrides such as maleicanhydride and itaconic anhydride; vinyl benzyl halides such as vinylbenzyl chloride and vinyl benzyl bromide; alkyl acrylates andmethacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate,lauryl acrylate, methyl methacrylate, ethyl methacrylate, butylmethacrylate, and lauryl methacrylate; and ethylenically unsaturatedoxiranes, such as glycidyl acrylate, glycidyl methacrylate, and glycidylethacrylate. Preferred ethylenically unsaturated amine-reactivecompounds include maleic anhydride, acrylic acid, methacrylic acid,glycidyl acrylate, glycidyl methacrylate, with maleic anhydride beingmore preferred. Polypropylene grafted with maleic anhydride is a morepreferred modified polymeric hydrocarbon.

The degree of incorporation or grafting of the reactive group is“application dependent,” but is preferably not more than 10 weightpercent, more preferably not more than 5 weight percent, more preferablynot more than 2 weight percent, and most preferably not more than 1weight percent; and preferably not less than 0.01 weight percent, morepreferably not less than 0.1 weight percent, and most preferably notless than 0.2 weight percent, based on the weight of the grafting agent.

A thermal grafting process is one method for reaction; however, othergrafting process may be used, such as photo initiation, includingdifferent forms of radiation, e-beam, or redox radical generation. Thefunctionalization may also occur at the terminal unsaturated group(e.g., vinyl group) or an internal unsaturation group, when such groupsare present in the polymer.

In accordance with some embodiments of this invention, the polymers withunsaturation are functionalized, for example, with carboxylic acidproducing moieties (preferably acid or anhydride moieties) selectivelyat sites of carbon-to-carbon unsaturation on the polymer chains,preferably in the presence of a free-radical initiator, to randomlyattach carboxylic acid producing moieties, i.e., acid or anhydride oracid ester moieties, onto the polymer chains.

The amine-reactive group or hydroxyl-reactive group can be grafted tothe polymer by any conventional method, typically in the presence of afree radical initiator, for example peroxides and azo compounds, or byionizing radiation. Organic initiators are preferred, such as any one ofthe peroxide initiators, for example, dicumyl peroxide, di-tert-butylperoxide, t-butyl perbenzoate, benzoyl peroxide, cumene hydroperoxide,t-butyl peroctoate, methyl ethyl ketone peroxide,2,5-dimethyl-2,5-di(tert-butyl peroxy)hexane, lauryl peroxide, andtert-butyl peracetate, t-butyl α-cumyl peroxide, di-t-butyl peroxide,di-t-amyl peroxide, t-amyl peroxybenzoate,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane,α,α′-bis(t-butylperoxy)-1,3-diisopropylbenzene,αα′-bis(t-butylperoxy)-1,4-diisopropylbenzene,2,5-bis(t-butylperoxy)-2,5-dimethylhexane, and2,5-bis(t-butylperoxy)-2,5-dimethyl-3-hexyne. A suitable azo compound isazobisisobutyl nitrite.

The grafting reaction should be performed under conditions that maximizegrafts onto the olefin multiblock interpolymer backbone, and minimizeside reactions, such as the homopolymerization of the grafting agent,which is not grafted to the olefin multiblock interpolymer. The graftingreaction may be performed in the melt, in solution, in the solid-state,in a swollen-state, and is preferably performed in the melt. Thegrafting reaction may be performed in a wide-variety of equipment, suchas, but not limited to, twin screw extruders, single screw extruders,Brabenders, and batch reactors.

It has been found that mixing the resin with the grafting agent andinitiator in the first stage of an extruder, at melt temperaturestypically from 120° C. to 260° C., preferably from 130° C. to 250° C.,has produced sufficiently grafted polymers. All individual temperaturevalues and ranges from 120° C. to 260° C. are included herein anddisclosed herein.

b) In-Situ Amine Functionalization and In-Situ HydroxylFunctionalization

The process to produce amino-functionalize or hydroxy-functionalizedolefin multiblock interpolymer can be carried out as one extrusion step,i.e. maleic anhydride can be grafted to the olefin multiblockinterpolymer in the first section of the extruder, followed byimidization with either a primary-secondary diamine or alkanolamine inthe latter section before pelletization.

Alternatively, two extruders, or melt mixing devises could be operatedin series to carry out both chemical steps.

In order to prepare an amino-functionalized olefin multiblockinterpolymer, without competing crosslinking reactions, in the melt,from anhydride-grafted olefin multiblock interpolymer, it is necessaryto employ a primary-secondary diamine of the general formulaH²N—R—NH—R″, where R is at least a C2 hydrocarbyl radical. The diaminecan be used in a stoichiometric excess or stoichiometric equivalence.

Suitable primary-secondary diamines include compounds of structure (I)below:H₂N—R₁—NH—R₂  (I).

In structure (I), R₁ is a divalent hydrocarbon radical, and preferably alinear hydrocarbon of the formula —(CH₂)_(n)—, where n is greater than,or equal to, 2, and preferably n is from 2 to 10, more preferably from 2to 8, and even more preferably from 2 to 6. R₂ is a monovalenthydrocarbon radical comprising at least 2 carbon atoms, and optionallymay be substituted with a heteroatom comprising group, such as OH or SH.Preferably R2 a linear hydrocarbon of the formula —(CH₂)_(n)—CH₃, wheren is from 1 to ten, and preferably n is from 1 to 9, more preferablyfrom 1 to 7, and even more preferably from 1 to 5.

Additionally primary-secondary diamines include, but are not limited toN-ethylethylenediamine, N-phenylethylenediamine,N-phenyl-1,2-phenylenediamine, N-phenyl-1,4-phenylenediamine, andN-(2-hydroxyethyl)-ethylenendiamine. Examples of preferredprimary-secondary diamines are shown below.

The alkanolamine is a compound comprising an amine group and at leastone hydroxyl group, preferably only one hydroxyl group. The amine can bea primary or a secondary amine, and is preferably a primary amine. Thepolyamine is a compound that contains at least two amine groups,preferably only two amine groups.

Suitable alkanolamines are those of structure (II) below:H₂N—R₁—OH  (II).

In structure (II), R₁ is a divalent hydrocarbon radical, and preferablya linear hydrocarbon of the formula —(CH₂)_(n)—, where n is greaterthan, or equal to, 2, and preferably n is from 2 to 10, more preferablyfrom 2 to 8, and even more preferably from 2 to 6.

Additional alkanolamines include, but are not limited to, ethanolamine,2-amino-1-propanol, 3-amino-1-propanol, 2-amino-1-butanol and2-aminobenzyl alcohol.

Examples of preferred alkanolamines are shown below.

Additional examples of suitable alkanolamines and suitable diamines arerepresented by the following formula (III):

In formula (III), X is O or NR′ (R′ is alkyl), and R is independently H,CH₃, or CH₂CH₃; and n is from 0 to 50. The disclosure and preparation ofhydroxyl amines can be found in U.S. Pat. Nos. 3,231,619; 4,612,335, and4,888,446, which teachings are incorporated herein by reference.Examples of preferred alkanolamines include 2-aminoethanol,1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol,2-(2-aminoethoxy)ethanol, 1-amino-2-butanol, 2-amino-3-butanol, andpolyoxyalkylene glycol amines. A preferred alkanolamine is2-aminoethanol.

In one embodiment, a maleic anhydride olefin multiblock interpolymer isfunctionalized with a primary-secondary diamine or with an alkanolamine.

In a further embodiment, the level of maleic anhydride used, is from0.10 weight percent to 5.0 weight percent, preferably from 0.50 weightpercent to 3.0 weight percent, and more preferably from 1.0 weightpercent to 2.0 weight percent, based on the weight of theunfunctionalized grafted olefin multiblock interpolymer.

In a further embodiment, the level of peroxide used, is from 0.01 weightpercent to 0.5 weight percent, preferably from 0.05 weight percent to0.3 weight percent, and more preferably from 0.1 weight percent to 0.2weight percent, based on the weight of the unfunctionalized graftedolefin multiblock interpolymer.

In yet a further embodiment, the level of primary-secondary diamine oralkanolamine used, is from 1 to 10 mole equivalents, preferably from 2to 8 mole equivalents, and more preferably from 4 to 6 mole equivalentsof amine, relative to grafted anhydride.

II. In-situ Functionalization Reactions Using Maleamic Acid

Hydroxy- and amino-functionalized olefin multiblock interpolymers, e.g.,ethylene-octene copolymers, can also be prepared in one step byperoxide-initiated grafting of the corresponding maleamic acids, orderivative thereof, which is formed by reaction of maleic anhydride andalkanolamine or primary-secondary diamine.

Maleamic acids are shown in Structure (IV) below:

In structure (IV), R1 and R2 are, independently, either hydrogen or aC1-C20 hydrocarbyl radical, which is linear or branched; R3 is hydrogenor a C1-C20 hydrocarbyl radical, which is linear or branched; R4 is ahydrocarbyl di-radical, which is linear or branched; X is OH or NHR₅,where R5 is a hydrocarbyl radical, which linear or branched, or ahydroxyethyl group. In a preferred embodiment, R1 and R2 are,independently, either hydrogen, or a C1-C10, preferably a C1-C8, andmore preferably a C1-C6, hydrocarbyl radical, which is linear orbranched. In a preferred embodiment, R3 is either hydrogen, or a C1-C10,preferably a C1-C8, and more preferably a C1-C6, hydrocarbyl radical,which is linear or branched. In a preferred embodiment, R4 is a C1-C20,preferably a C1-C10, and more preferably a C1-C8, and even morepreferably a C1-C6 hydrocarbyl radical, which is linear or branched.

In a preferred embodiment, R5 is a C1-C20, preferably a C1-C10, and morepreferably a C1-C8, and even more preferably a C1-C6 hydrocarbylradical, which is linear or branched. In another embodiment, R5 is alinear —(CH₂)_(n)—CH₃, where n is greater than, or equal to 1, andpreferably n is from 1 to 9, more preferably from 1 to 7, and even morepreferably from 1 to 5. Additional examples of R5, include, but are notlimited to, the following structures: —CH₃, —CH₂CH₃, —CH₂CH₂CH₃,—CH₂CH₂CH₂CH₃, —CH₂(CH₃)CH₃, —CH₂(CH₃)CH₂CH₃, —CH₂CH₂(CH₃)CH₃,—CH₂(CH₃)CH₂CH₂CH₃, —CH₂CH₂(CH₃)CH₂CH₃, and —CH₂CH₂CH₂(CH₃)CH₃.

Additional maleamic acid structures are shown below. In each structure,R3 and R4 are defined as above.

Preferably the maleamic acid, is shown in structure (V) below:

The olefin multiblock interpolymer is functionalized with a maleamicacid as shown in structure (V). In one embodiment, the level of maleamicacid used, is from 0.10 weight percent to 5.0 weight percent, preferablyfrom 0.50 weight percent to 3.0 weight percent, and more preferably from1.0 weight percent to 2.0 weight percent, based on the weight of theunfunctionalized grafted olefin multiblock interpolymer.

In a further embodiment, the level of peroxide used, is from 0.01 weightpercent to 0.5 weight percent, preferably from 0.05 weight percent to0.3 weight percent, and more preferably from 0.1 weight percent to 0.2weight percent of the unfunctionalized grafted olefin multiblockinterpolymer.

In a further embodiment, the level of peroxide used, is from 0.01 weightpercent to 1 weight percent, preferably from 0.01 weight percent to 0.5weight percent, and more preferably from 0.05 weight percent to 0.3weight percent, and even more preferably from 0.1 weight percent to 0.2weight percent, based on the amount of unfunctionalized grafted olefinmultiblock interpolymer.

III. Diamine Imbibe Process

The olefin multiblock interpolymers as described herein may also befunctionalized using a diamine imbibing process. Here, an olefinmultiblock interpolymer is first functionalized with a group reactivewith amine functionality. Preferably, the olefin multiblock interpolymeris functionalized with an anhydride group. At least one diamine is mixedwith the functionalized olefin multiblock interpolymer at a temperaturebelow the melting point of the olefin multiblock interpolymer, andpreferably at room temperature. The diamine is allowed to absorb orimbibe into the olefin multiblock interpolymer, and reacts with diaminereactive group to form a succinamic acid. The reaction of the diaminewith the diamine reactive functional group to form the imide ring, canthen be completed by subjecting the mixture to a thermal treatment, suchas in a melt extrusion process. Suitable diamines include those diaminesdiscussed herein. The imbibing process helps to ensure that the diamineis thoroughly mixed with the olefin multiblock interpolymer for anefficient functionalization reaction.

Suitable primary-secondary diamines include compounds of structure (VI)below:H₂N—R₁—NH—R₂  (VI).

In structure (I), R₁ is a divalent hydrocarbon radical, and preferably alinear hydrocarbon of the formula —(CH₂)_(n)—, where n is greater than,or equal to, 2, and preferably n is from 2 to 10, more preferably from 2to 8, and even more preferably from 2 to 6. R₂ is a monovalenthydrocarbon radical comprising at least 2 carbon atoms, and optionallymay be substituted with a heteroatom containing group, such as OH or SH.Preferably R2 a linear hydrocarbon of the formula —(CH₂)_(n)—CH₃, wheren is from 0 to ten, and preferably n is from 0 to 9, more preferablyfrom 0 to 7, and even more preferably from 0 to 5.

Suitable primary-secondary diamines include, but are not limited to,N-methyl-ethylenediamine, N-ethylethylenediamine,N-phenylethylenediamine, N-methyl-1,3-propanediamine,N-methylenediamine, N-phenyl-1,2-phenylenediamine,N-phenyl-1,4-phenylenediamine, 1-(2-aminoethyl)-piperazine, andN-(2-hydroxyethyl)-ethylenediamine. Examples of preferredprimary-secondary diamines are shown below.

IV. Olefin Multiblock Interpolymers Used as Base Polymer in the Graftingand Functionalization Reactions

The polyolefin used as a base polymer in the process entitled “I.In-situ Functionalization Reactions using of a Grafted Olefin multiblockinterpolymer”, “II. In-situ Functionalization Reactions using MaleamicAcid”, and “III. Diamine Imbibe Process” above typically comprises anolefin multiblock interpolymer, preferably ethylene/α-olefin multiblockinterpolymer, wherein the interpolymer has one or more of the followingcharacteristics:

(1) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or

(2) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1; or

(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)²; or

(4) an Mw/Mn from about 1.7 to about 3.5, and is characterized by a heatof fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsiusdefined as the temperature difference between the tallest DSC peak andthe tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH havethe following relationships:

ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,

ΔT≧48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(5) an elastic recovery, Re, in percent at 300 percent strain and 1cycle measured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d); or

(6) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene interpolymer fraction eluting between the sametemperatures, wherein said comparable random ethylene interpolymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isin the range of about 1:1 to about 9:1.

The olefin multiblock interpolymers typically comprise ethylene and oneor more copolymerizable α-olefin comonomers in polymerized form,characterized by multiple blocks or segments of two or more polymerizedmonomer units differing in chemical or physical properties. That is, theolefin multiblock interpolymers, preferably ethylene/α-olefininterpolymers, are block interpolymers, preferably multiblockinterpolymers or copolymers. The terms “interpolymer” and copolymer” areused interchangeably herein. In some embodiments, the multiblockcopolymer can be represented by the following formula:(AB)_(n)where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher. “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.AAA-AA-BBB-BB

In still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multiblock polymers typically comprise various amounts of “hard” and“soft” segments. “Hard” segments refer to blocks of polymerized units inwhich ethylene is present in an amount greater than about 95 weightpercent, and preferably greater than about 98 weight percent based onthe weight of the polymer. In other words, the comonomer content(content of monomers other than ethylene) in the hard segments is lessthan about 5 weight percent, and preferably less than about 2 weightpercent based on the weight of the polymer. In some embodiments, thehard segments comprises all or substantially all ethylene. “Soft”segments, on the other hand, refer to blocks of polymerized units inwhich the comonomer content (content of monomers other than ethylene) isgreater than about 5 weight percent, preferably greater than about 8weight percent, greater than about 10 weight percent, or greater thanabout 15 weight percent based on the weight of the polymer. In someembodiments, the comonomer content in the soft segments can be greaterthan about 20 weight percent, greater than about 25 weight percent,greater than about 30 weight percent, greater than about 35 weightpercent, greater than about 40 weight percent, greater than about 45weight percent, greater than about 5 weight percent, or greater thanabout 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 5 weight percent to about95 weight percent, from about 10 weight percent to about 90 weightpercent, from about 15 weight percent to about 85 weight percent, fromabout 20 weight percent to about 80 weight percent, from about 25 weightpercent to about 75 weight percent, from about 30 weight percent toabout 70 weight percent, from about 35 weight percent to about 65 weightpercent, from about 40 weight percent to about 60 weight percent, orfrom about 45 weight percent to about 55 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR. Such methods and calculations are disclosed in aconcurrently filed U.S. patent application Ser. No. 11/376,835, entitled“Ethylene/α-Olefin Block Interpolymers”, filed on Mar. 15, 2006, in thename of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to DowGlobal Technologies Inc., the disclose of which is incorporated byreference herein in its entirety.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) ad determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

The term “olefin multiblock interpolymer”, “multiblock copolymer” or“segmented copolymer” refers to a polymer comprising two or morechemically distinct regions or segments (referred to as “blocks”)preferably joined in a linear manner, that is, a polymer comprisingchemically differentiated units which are joined end-to-end with respectto polymerized ethylenic functionality, rather than in pendent orgrafted fashion. In a preferred embodiment, the blocks differ in theamount or type of comonomer incorporated therein, the density, theamount of crystallinity, the crystallite size attributable to a polymerof such composition, the type or degree of tacticity (isotactic orsyndiotactic), regio-regularity or regio-irregularity, the amount ofbranching including long chain branching or hyper-branching, thehomogeneity, or any other chemical or physical property. The multiblockcopolymers are characterized by unique distributions of bothpolydispersity index (PDI or Mw/Mn), block length distribution, and/orblock number distribution due to the unique process making of thecopolymers. More specifically, when produced in a continuous process,the polymers desirably possess PDI from 1.7 to 2.9, preferably from 1.8to 2.5, more preferably from 1.8 to 2.2, and most preferably from 1.8 to2.1. When produced in a batch or semi-batch process, the polymerspossess PDI from 1.0 to 2.9, preferably from 1.3 to 2.5, more preferablyfrom 1.4 to 2.0, and most preferably from 1.4 to 1.8.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R¹+k*(R^(U)−R^(L)), wherein k is a variable ranging from 1percent to 100 percent with a 1 percent increment, i.e., k is 1 percent,2 percent, 3 percent, 4 percent, 5 percent . . . , 50 percent, 51percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

The ethylene/α-olefin interpolymers used in embodiments of the invention(also sometimes referred to as “inventive interpolymer” or “inventivepolymer”) comprise ethylene and one or more copolymerizable α-olefincomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (block interpolymer), preferably a multiblockcopolymer. The ethylene/α-olefin interpolymers are characterized by oneor more of the aspects described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:

T_(m)>−2002.9−4538.5(d)−2422.2(d)², and preferably

T_(m)≧−62888.1+1314(d)−6720.3(d)², and more preferably

T_(m)≧858.21−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning Calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:

ΔT>−0.1299(ΔH)+62.81, and preferably

ΔT≧−0.1299(ΔH)+64.38, and more preferably

ΔT≧−0.1299(ΔH)+65.95.

for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299(ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recover, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:

Re>1481−1629(d); and preferably

Re≧1491−1629(d); and more preferably

Re≧1501−1629(d); and even more preferably

Re≧1511−1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 10 MPa, preferably a tensile strength≧11 MPa, morepreferably a tensile strength≧13 MPa and/or an elongation at break of atleast 600 percent, more preferably at least 700 percent, highlypreferably at least 800 percent, and most highly preferably at least 900percent at a crosshead separation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio G′(25° C.)/G′(100° C.), of from 1 to 50,preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot² (4800 Pa), preferably equal to or lessthan 50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft²(240 Pa), and as low as 0 lbs/ft² (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close zero percent.

In some embodiments, the multiblock copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmultiblock copolymers are those comprising 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer desirably is firstfractionated using TREF into fractions each having an eluted temperaturerange of 10° C. or less. That is, each eluted fraction has a collectiontemperature window of 10° C. or less. Using this technique, said blockinterpolymers have at least one such fraction having a higher molarcomonomer content than a corresponding fraction of the comparableinterpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multiblock copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,but dividing the peak height by two, and then drawing a line horizontaltot he base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHMmethyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymers has highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity(−0.2013)T+20.07, more preferably greater than or equal to the quantity(−0.2013)T+21.07, where T is the numerical value of the peak elutiontemperature of the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013)T+20.07 (solid line). The line for the equation(−0.2013)T+21.07 is depicted by a dotted line. Also depicted are thecomonomer contents for fractions of several block ethylene/1-octeneinterpolymers of the invention (multiblock copolymers). All of the blockinterpolymer fractions have significantly higher 1-octene content thaneither line at equivalent elution temperatures. This result ischaracteristic of the inventive interpolymer and is believed to be dueto the presence of differentiated blocks within the polymer chains,having both crystalline and amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and comparative F to be discussed below.The peak eluting from 40 to 130° C., preferably from 60° C. to 95° C.for both polymers is fractionated into three parts, each part elutingover a temperature range of less than 10° C. Actual data for Example 5is represented by triangles. The skilled artisan can appreciate that anappropriate calibration curve may be constructed for interpolymerscomprising different comonomers and a line used as a comparison fittedto the TREF values obtained from comparative interpolymers of the samemonomers, preferably random copolymers made using a metallocene or otherhomogeneous catalyst composition. Inventive interpolymers arecharacterized by a molar comonomer content greater than the valuedetermined from the calibration curve at the same TREF elutiontemperature, preferably at least 5 percent greater, more preferably atleast 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multiblock copolymer, said block interpolymer having amolecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356)T+13.89, more preferably greater than or equal to the quantity(−0.1356)T+14.93, and most preferably greater than or equal to thequantity (−0.2013)T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

Preferably, for the above interpolymers of ethylene and at least onealpha-olefin especially those interpolymers having a whole polymerdensity from about 0.855 to about 0.935 g/cm³, and more especially forpolymers having more than about 1 mole percent comonomer, the blockedinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity(−0.2013)T+20.07, more preferably greater than or equal to the quantity(−0.2013)T+21.07, where T is the numerical value of the peak elutiontemperature of the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multiblock copolymer, said block interpolymer having amolecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mol percentcomonomer, has a DSC melting point that corresponds to the equation:Tm≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amultiblock copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char. Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₂) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying a thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infrared detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatograph-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”. Polymeric Materials Science and Engineering (1991), 65,98-100; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, both ofwhich are incorporated by reference herein in their entirety.

In other embodiments, the inventive ethylene/α-olefin interpolymer ischaracterized by an average block index, ABI, which is greater than zeroand up to about 1.0 and a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. The average block index, ABI, is the weightaverage of the block index (“BI”) for each of the polymer fractionsobtained in preparative TREF from 20° C. and 110° C., with an incrementof 5° C.:ABI=Σ(w _(i) BI _(i))where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction.

For each polymer fraction BI is defined by one of the two followingequations (both of which give the same BI value):

${BI} = {{\frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}\mspace{14mu}{or}\mspace{14mu}{BI}} = {- \frac{{LnP}_{X} - {LnP}_{XO}}{{LnP}_{A} - {LnP}_{AB}}}}$where T_(X) is the preparative ATREF elution temperature for the ithfraction (preferably expressed in Kelvin), P_(X) is the ethylene molefraction for the ith fraction, which can be measured by NMR or IR asdescribed above. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As a first orderapproximation, the T_(A) and P_(A) values are set to those for highdensity polyethylene homopolymer, if the actual values for the “hardsegments” are not available. For calculations performed herein, T_(A) is372° K., P_(A) is 1.

T_(AB) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(AB). T_(AB) canbe calculated from the following equation:LnP _(AB) =α/T _(AB)+βwhere α and β are two constants which can be determined by calibrationusing a number of known random ethylene copolymers. It should be notedthat α and β may vary from instrument to instrument. Moreover, one wouldneed to create their own calibration curve with the polymer compositionof interest and also in a similar molecular weight range as thefractions. There is a slight molecular weight effect. If the calibrationcurve is obtained from similar molecular weight ranges, such effectwould be essentially negligible. In some embodiments, random ethylenecopolymers satisfy the following relationship:LnP=−237.83/T _(ATREF)+0.639T_(XO) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(X). T_(XO) can becalculated from LnP_(X)=α/T_(XO)+β. Conversely, P_(XO) is the ethylenemole fraction for a random copolymer of the same composition and havingan ATREF temperature of T_(X), which can be calculated fromLnP_(XO)=α/T_(X)+β.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.3 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction ahs a block index greater than about 0.1 and up to about1.0 and a molecular weight distribution, M_(w)/M_(n), greater than about1.3. In some embodiments, the polymer fraction has a block index greaterthan about 0.6 and up to about 1.0, greater than about 0.7 and up toabout 1.0, greater than about 0.8 and up to about 1.0, or greater thanabout 0.9 and up to about 1.0. In other embodiments, the polymerfraction has a block index greater than about 0.1 and up to about 1.0,greater than about 0.2 and up to about 1.0, greater than about 0.3 andup to about 1.0, greater than about 0.4 and up to about 1.0, or greaterthan about 0.4 and up to about 1.0. In still other embodiments, thepolymer fraction has a block index greater than about 0.1 and up toabout 0.5, greater than about 0.2 and up to about 0.5, greater thanabout 0.3 and up to about 0.5, or greater than about 0.4 and up to about0.5. In yet other embodiments, the polymer fraction has a block indexgreater than about 0.2 and up to about 0.9, greater than about 0.3 andup to about 0.8, greater than about 0.4 and up to about 0.7, or greaterthan about 0.5 and up to about 0.6.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C. more preferably lessthan −30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog(G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 90° C. as well as a flexural modulus of from 3 kpsi (20 MPa) to13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 104° C. as well as a flexural modulus of at least 3 kpsi (20MPa). They may be characterized as having an abrasion resistance (orvolume loss) of less than 90 mm³. FIG. 7 shows the TMA (1 mm) versusflex modulus for the inventive polymers, as compared to other knownpolymers. The inventive polymers have significantly betterflexibility-heat resistance balance than the other polymers.

Additionally, the ethylene/α-olefin interpolymers can have a meld indexI₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, I₂, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene comprisingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/566,62938, filed Mar. 17,2005; PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

-   -   (A) a first olefin polymerization catalyst having a high        comonomer incorporation index.    -   (B) a second olefin polymerization catalyst having a comonomer        incorporation index less than 90 percent, preferably less than        50 percent, most preferably less than 5 percent of the comonomer        incorporation index of catalyst (A), and    -   (C) a chain shuttling agent.

Representative catalysts and chain shuttling agent are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of US-A-2004/0010103.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include di(i-butyl)zinc,di(n-hexyl)zinc, triethylaluminum, trioctylaluminum, triethylgallium,i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminumbis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide),bis(n-octadecyl)i-butylaluminum, i-butylaluminum bis(di(n-pentyl)amide),n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminumdi(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide),ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multiblockcopolymers, preferably linear multiblock copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multiblock copolymers,especially linear multiblock copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer comprisingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, high recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers comprising the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree of level of blockiness. That is the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare high, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces high crystalline polymer is more susceptible tochain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multiblock copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds comprising vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphanolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymultiblock EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multiblock elastomeric polymers have an ethylene contentof from 60 to 90 percent, a diene content of from 0.1 to 10 percent, andan α-olefin content of from 10 to 40 percent, based on the total weightof the polymer. Preferred polymers are high molecular weight polymers,having a weight average molecular weight (Mw) from 10,000 to about2,500,000, preferably from 20,000 to 500,000, more preferably from20,000 to 350,000, and a polydispersity less than 3.5, more preferablyless than 3.0, and a Mooney viscosity (ML (1+4) 125° C.) from 1 to 250.More preferably, such polymers have an ethylene content from 65 to 75percent, a diene content from 0 to 6 percent, and an α-olefin contentfrom 20 to 35 percent.

The ethylene/α-olefin interpolymers useful in the processes describedabove in “I. In-situ Functionalization Reactions using of a GraftedOlefin multiblock interpolymer”, “II. In-situ FunctionalizationReactions using Maleamic Acid”, and/or “III. Diamine Imbibe Process” maybe partially functionalized so long as such functionalization does notinterfere with the process. Exemplary functional groups may include, forexample, ethylenically unsaturated mono- and di-functional carboxylicacids, ethylenically unsaturated mono- and di-functional carboxylic acidanhydrides, salts thereof and esters thereof. Such functional groups maybe grated to an ethylene/α-olefin interpolymer, or it may becopolymerized with ethylene and an optional additional comonomer to forman interpolymer of ethylene, the functional comonomer and optionallyother comonomer(s). Means for grafting functional groups ontopolyethylene are described for example in U.S. Pat. Nos. 4,762,890,4,927,888, and 4,950,541, the disclosures of these patents areincorporated herein by reference in their entirety. One particularlyuseful functional group is malic anhydride.

The amount of the functional group present is not so much that itinterferes with the inventive processes. Typically, the functional groupcan be present in an amount of at least about 1.0 weight percent,preferably at least about 5 weight percent, and more preferably at leastabout 7 weight percent. The functional group will typically be presentin a copolymer-type functionalized interpolymer in an amount less thanabout 40 weight percent, preferably less than about 30 weight percent,and more preferably less than about 25 weight percent.

Polyolefin Blends

In another embodiment of the invention, one or more polyolefins may bemixed or blended with the olefin multiblock interpolymers used as thebase polymer so that the blend is subject to the functionalizationreactions. The functionalized polymers of the invention may also be usedas a concentrate that can be mixed or blended with unfunctionalizedpolyolefin to achieve lower net levels of functionality in the finalproduct.

Ethylene-Based Polymers May be Blended with the Olefin MultiblockInterpolymer

As discussed above, suitable ethylene-base polymers may be mixed orblended with the olefin multiblock interpolymers used as the basepolymer and then the blend may be functionalized. Such polymers include,for example, high density polyethylene (HDPE), linear low densitypolyethylene (LLDPE), ultra low density polyethylene (ULDPE),homogeneously branched linear ethylene polymers, and homogeneouslybranched substantially linear ethylene polymers (that is homogeneouslybranched long chain branched ethylene polymers).

High density polyethylene (HDPE) typically has a density of about 0.94to about 0.97 g/cc. Commercial examples of HDPE are readily available inthe market. Other suitable ethylene polymers include low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), and linearvery low density polyethylene (VLDPE). Typically the low densitypolyethylene (LDPE) is made under high-pressure, using free-radicalpolymerization conditions. Low density polyethylene typically has adensity from 0.91 to 0.94 g/cc.

Linear low density polyethylene (LLDPE) is characterized by little, ifany, long chain branching, in contrast to conventional LDPE. The processfor producing LLDPE are well known in the art and commercial grades ofthis polyolefin resin are available. Generally, LLDPE is produced ingas-phase fluidized bed reactors or liquid phase solution processreactors, using a Ziegler-Natta catalyst system.

The linear low density polyethylene (LLDPE), ultra low densitypolyethylene (ULDPE), homogeneously branched linear ethyleneinterpolymers, or homogeneously branched substantially linear ethyleneinterpolymer, typically have polymerized therein at least one α-olefin.The term “interpolymer” used herein indicates the polymer can be acopolymer, a terpolymer or any polymer having more than one polymerizedmonomer. Monomers usefully copolymerized with ethylene to make theinterpolymer include the C3-C20 α-olefins, and especially propylene,1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and1-octene. Especially preferred comonomers include propylene, 1-butene,1-hexene and 1-octene.

Overall, suitable ethylene polymers have a melt index, I2, less than, orequal to, 1000 g/10 min. preferably less than, or equal to, 500 g/10min, more preferably less than, or equal to, 100 g/10 min, mostpreferably less than, or equal to, 50 g/10 min, as measured inaccordance with ASTM 1238, Condition 190° C./2.16 kg.

Commercial examples of suitable ethylene-base interpolymers includeATTANE™, AFFINITY™, DOWLEX™, ELITE™, all available from the Dow ChemicalCompany; and EXCEED™ and EXACT™ available from Exxon Chemical Company.

The terms “homogeneous” and “homogeneously-branched” are used inreference to an ethylene/α-olefin interpolymer, in which the α-olefincomonomer is randomly distributed within a given polymer molecule, andsubstantially all of the polymer molecules have the sameethylene-to-comonomer ratio. The homogeneously branched ethyleneinterpolymers that can be used in the practice of this invention includelinear ethylene interpolymers, and substantially linear ethyleneinterpolymers.

Included amongst the homogeneously branched linear ethyleneinterpolymers are ethylene polymers, which lack long chain branching,but do have short chain branches, derived from the comonomer polymerizedinto the interpolymer, and which are homogeneously distributed, bothwithin the same polymer chain, and between different polymer chains.That is, homogeneously branched linear ethylene interpolymers lack longchain branching, just as is the case for the linear low densitypolyethylene polymers or linear high density polyethylene polymers, madeusing uniform branching distribution polymerization processes, asdescribed, for example, by Elston in U.S. Pat. No. 3,645,992. Commercialexamples of homogeneously branched linear ethylene/α-olefininterpolymers include TAFMER™ polymers supplied by the Mitsui ChemicalCompany and EXACT™ polymers supplied by ExxonMobil Chemical Company.

The substantially linear ethylene interpolymers used in the presentinvention are described in U.S. Pat. Nos. 5,272,236; 5,278,272;6,054,544; 6,335,410 and 6,723,810; the entire contents of each areherein incorporated by reference. The substantially linear ethyleneinterpolymers are those in which the comonomer is randomly distributedwithin a given interpolymer molecule, and in which substantially all ofthe interpolymer molecules have the same ethylene/comonomer ratio withinthat interpolymer. In addition, the substantially linear ethyleneinterpolymers are homogeneously branched ethylene interpolymers havinglong chain branching. The long chain branches have the same comonomerdistribution as the polymer backbone, and can have about the same lengthas the length of the polymer backbone. “Substantially linear,”typically, is in reference to a polymer that is substituted, on average,with 0.01 long chain branches per 1000 total carbons (including bothbackbone and branch carbons) to 3 long chain branches per 1000 totalcarbons. The length of a long chain branch is longer than the carbonlength of a short chain branch formed from the incorporation of onecomonomer into the polymer backbone.

Some polymers may be substituted with 0.01 long chain branches per 1000total carbons to 1 long chain branch per 1000 total carbons, or from0.05 long chain branches per 1000 total carbons to 1 long chain branchper 1000 total carbons, and especially from 0.3 long chain branches per1000 total carbons to 1 long chain branch per 1000 total carbons.Commercial examples of substantially linear polymers include the ENGAGE™polymers and AFFINITY™ polymers (both available from The Dow ChemicalCompany).

The substantially linear ethylene interpolymers form a unique class ofhomogeneously branched ethylene polymers. They differ substantially fromthe well-known class of conventional, homogeneously branched linearethylene interpolymers, described by Elston in U.S. Pat. No. 3,645,992,and, moreover, they are not in the same class as conventionalheterogeneous Ziegler-Natta catalyst polymerized linear ethylenepolymers (for example, ultra low density polyethylene (ULDPE), linearlow density polyethylene (LLDPE) or high density polyethylene (HDPE)made, for example, using the technique disclosed by Anderson et al. inU.S. Pat. No. 4,076,698); nor are they in the same class as highpressure, free-radical initiated, highly branched polyethylenes, suchas, for example, low density polyethylene (LDPE), ethylene-acrylic acid(EAA) copolymers and ethylene vinyl acetate (EVA) copolymers.

The homogeneously branched, substantially linear ethylene interpolymersuseful in the invention have excellent processability, even though theyhave a relatively narrow molecular weight distribution. Surprisingly,the melt flow ratio (I₁₀/I₂), according to ASTM D 1238, of thesubstantially linear ethylene interpolymers can be varied widely, andessentially independently of the molecular weight distribution(M_(w)/M_(n) or MWD). This surprising behavior is completely contrary toconventional homogeneously branched linear ethylene interpolymers, suchas those described, for example, by Elston in U.S. Pat. No. 3,645,992,and heterogeneously branched conventional Ziegler-Natta polymerizedlinear polyethylene interpolymers, such as those described, for example,by Anderson et. al., in U.S. Pat. No. 4,076,698. Unlike substantiallylinear ethylene interpolymers, linear ethylene interpolymers (whetherhomogeneously or heterogeneously branched) have rheological properties,such that, as the molecular weight distribution increases, the I₁₀/I₂value also increases.

“Long chain branching (LCB)” can be determined by conventionaltechniques known in the industry, such as ¹³C nuclear magnetic resonance(¹³C NMR) spectroscopy, using, for example, the method of Randall (Rev.Micromole. Chem. Phys., C29 (2&3), p. 285-297). Two other methods aregel permeation chromatography, coupled with a low angle laser lightscattering detector (GPC-LALLS), and gel permeation chromatography,coupled with a differential viscometer detector (GPC-DV). The use ofthese techniques for long chain branch detection, and the underlyingtheories, have been well documented in the literature. See, for example,Zimm, B. H. and Stockmayer, W. H., J. Chem. Phys., 17, 1301 (1949) andRudin A., Modern Methods of Polymer Characterization, John Wiley & Sons,New York (1991) pp. 103-112.

In contrast to “substantially linear ethylene polymer,” “linear ethylenepolymer” means that the polymer lacks measurable or demonstrable longchain branches, that is, typically, the polymer is substituted with anaverage of less than 0.01 long chain branch per 1000 total carbons.

The homogeneous branched ethylene polymers useful in the presentinvention will preferably have a single melting peak, as measured usingdifferential scanning calorimetry (DSC), in contrast to heterogeneouslybranched linear ethylene polymers, which have 2 or more melting peaks,due to the heterogeneously branched polymer's broad branchingdistribution.

Homogeneously branched linear ethylene interpolymers are a known classof polymers which have a linear polymer backbone, no measureable longchain branching and a narrow molecular weight distribution. Suchpolymers are interpolymers of ethylene and at least one α-olefincomonomer of from 3 to 20 carbon atoms, and are preferably copolymers ofethylene with a C3-C20 a-olefin, and are more preferably copolymers ofethylene with propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or1-octene, and even more preferably, propylene, 1-butene, 1-hexene or1-octene.

This class of polymers is disclosed for example, by Elston in U.S. Pat.No. 3,645,992, and subsequent processes to produce such polymers usingmetallocene catalysts have been developed, as shown, for example, in EP0 129 368, EP 0 260 999, U.S. Pat. No. 4,701,432; U.S. Pat. No.4,937,301; U.S. Pat. No. 4,935,397; U.S. Pat. No. 5,055,438; and WO90/07526, and others. The polymers can be made by conventionalpolymerization process (for example, gas phase, slurry, solution, andhigh pressure).

In one embodiment, the ethylene/α-olefin interpolymer has a molecularweight distribution (M_(w)/M_(n)) less than, or equal to, 10, andpreferably less than, or equal to, 5. More preferably theethylene/α-olefin polymers have a molecular weight distribution from 1.1to 5, and more preferably from 1.5 to 4. All individual values andsubranges from 1 to 5 are included herein and disclosed herein.

Comonomers include, but are not limited to, propylene, isobutylene,1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene, non-conjugated dienes, polyenes, butadienes, isoprenes,pentadienes, hexadienes (for example, 1,4-hexadiene), octadienes,styrene, halo-substituted styrene, alkyl-substituted styrene,tetrafluoroethylenes, vinylbenzocyclobutene, haphthenics, cycloalkenes(for example, cyclopentene, cyclohexene, cyclooctene), and mixturesthereof. Typically and preferably, the ethylene is copolymerized withone C₃-C₂₀ α-olefin. Preferred comonomers include propene, 1-butene,1-pentene, 1-hexene, 1-heptene and 1-octene, and more preferably includepropene, 1-butene, 1-hexene and 1-octene.

Illustrative α-olefins include propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene and 1-decene. Theα-olefin is desirably a C3-C10 α-olefin. Preferably, the α-olefin ispropylene, 1-butene, 1-hexene or 1-octene. Illustrative interpolymersinclude ethylene/propylene (EP) copolymers, ethylene/butene (EB)copolymers, ethylene/hexene (EH) copolymers, ethylene/octene (EO)copolymers, ethylene/α-olefin/diene modified (EAODM) interpolymers, suchas ethylene/propylene/diene modified (EPDM) interpolymers andethylene/propylene/octene terpolymers. Preferred copolymers include EP,EB, EH and EO polymers.

Suitable diene and triene comonomers include 7-methyl-1,6-octadiene;3,7-dimethyl-1,6-octadiene; 5,7-dimethyl-1,6-octadiene;3,7,11-trimethyl-1,6,10-octatriene; 6-methyl-1,5heptadiene;1,3-butadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene;1,9-decadiene; 1,10-undecadiene; norbornene; tetracyclododecene; ormixtures thereof; and preferably butadiene; hexadienes; and octadienes;and most preferably 1,4-hexadiene; 1,9-decadiene;4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; dicyclopentadiene; and5-ethylidene-2-norbornene (ENB).

Additional unsaturated comonomers include 1,3-butadiene, 1,3-pentadiene,norbornadiene, and dicyclopentadiene; C8-40 vinyl aromatic compoundsincluding styrene, o-, m-, and p-methylstyrene, divinylbenzene,vinylbiphenyl, vinylnapthalene; and halogen-substituted C8-40 vinylaromatic compounds such as chlorostyrene and fluorostyrene.

In another embodiment, the ethylene/α-olefin interpolymer has a meltindex (I₂) from 0.01 g/10 min to 1000 g/10 min, preferably from 0.01g/10 min to 500 g/10 min, and more preferably from 0.01 g/10 min to 100g/10 min, as determined using ASTM D-1238 (190° C., 2.16 kg load). Allindividual values and subranges from 0.01 g/10 min to 1000 g/10 min areincludes herein and disclosed herein.

In another embodiment, the ethylene/α-olefin interpolymer has a percentcrystallinity of less than, or equal to, 60 percent, preferably lessthan, or equal to, 50 percent, and more preferably less than, or equalto, 40 percent, as measured by DSC. Preferably, these polymers have apercent crystallinity from 2 percent to 60 percent, including allindividual values and subranges from 2 percent to 60 percent. Suchindividual values and subranges are disclosed herein.

In another embodiment, the ethylene/α-olefin interpolymer has a densityless than, or equal to, 0.93 g/cc, preferably less than, or equal to,0.92 g/cc, and more preferably less than, or equal to 0.91 g/cc. Inanother embodiment, the ethylene/α-olefin interpolymer has a densitygreater than, or equal to, 0.85 g/cc, preferably greater than, or equalto, 0.86 g/cc, and more preferably greater than, or equal to, 0.87 g/cc.

In another embodiment, the ethylene/α-olefin interpolymer has a densityfrom 0.85 g/cm³ to 0.93 g/cm³, and preferably from 0.86 g/cm³ to 0.92g/cm³, and more preferably from 0.87 g/cm³ to 0.91 g/cm³. All individualvalues and subranges from 0.85 g/cm³ to 0.93 g/cm³ are included hereinand disclosed herein.

In another embodiment, the final functionalized ethylene/α-olefininterpolymer, comprising an imide functionality, has a melt index (I₂)from 0.01 g/10 min to 1000 g/10 min, preferably from 0.01 g/10 min to500 g/10 min, and more preferably from 0.01 g/10 min to 100 g/10 min, asdetermined using ASTM D-1238 (190° C., 2.16 kg load). All individualvalues and subranges from 0.01 g/10 min to 1000 g/10 min are includesherein and disclosed herein.

Propylene-Based Polymers May be Blended with the Olefin MultiblockInterpolymer

As discussed above, suitable propylene-based interpolymers may be mixedor blended with the olefin multiblock interpolymer used as the basepolymer and then the blend may be functionalized. Suitablepropylene-based interpolymers include propylene homopolymers, propyleneinterpolymers, as well as reactor copolymers of polypropylene (RCPP),which can contain about 1 to about 20 wt % ethylene or an α-olefincomonomer of 4 to 20 carbon atoms. The polypropylene homopolymer can beisotactic, syndiotactic or atactic polypropylene. The propyleneinterpolymer can be a random or block copolymer, or a propylene-basedterpolymer.

The propylene polymer may be crystalline, semi-crystalline or amorphous.A crystalline polypropylene polymer typically has at least 90 molepercent of its repeating units derived from propylene, preferably atleast 97 percent, more preferably at least 99 percent.

Suitable comonomers for polymerizing with propylene include ethylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-unidecene, 1dodecene, as well as 4-methyl-1-pentene,4-methyl-1-hexene, 5-methyl-1-hexene, vinylcyclohexane, and styrene. Thepreferred comonomers include ethylene, 1-butene, 1-hexene, and 1-octene,and more preferably ethylene.

Optionally, the propylene-based polymer comprises monomers having atleast two double bonds which are preferably dienes or trienes. Suitablediene and triene comonomers include 7-methyl-1,6-octadiene;3,7-dimethyl-1,6-octadiene; 5,7-dimethyl-1,6-octadiene;3,7,11-trimethyl-1,6,10-octatriene; 6-methyl-1,5heptadiene;1,3-butadiene; 1,6-heptadiene; 1,7-octadiene; 1,8-nonadiene;1,9-decadiene; 1,10-undecadiene; norbornene; tetracyclododecene; ormixtures thereof; and preferably butadiene; hexadienes; and octadienes;and most preferably 1,4-hexadiene; 1,9-decadiene;4-methyl-1,4-hexadiene; 5-methyl-1,4-hexadiene; dicyclopentadiene; and5-ethylidene-2-norbornene (ENB).

Additional unsaturated comonomers include 1,3-butadiene, 1,3-pentadiene,norbornadiene, dicylopentadiene; C8-40 vinyl aromatic compoundsincluding styrene, o-, m-, and p-methylstyrene, divinylbenzene,vinylbiphenyl, vinylnapthalene; and halogen-substituted C8-40 vinylaromatic compounds such as chlorostyrene and fluorostyrene.

The propylene copolymers of particular interest includepropylene/ethylene, propylene/1-butene, propylene/1-hexene,propylene/4-methyl-1-pentene, propylene/1-octene,propylene/ethylene/1-butene, propylene/ethylene/ENB,propylene/ethylene/1-hexene, propylene/ethylene/1-octene,propylene/styrene, and propylene/ethylene/styrene.

Suitable polypropylenes are formed by means within the skill in the art,for example, using single site catalysts (metallocene or constrainedgeometry) or Ziegler Natta catalysts. The propylene and optionalcomonomers, such as ethylene or alpha-olefin monomers are polymerizedunder conditions within the sill in the art, for instance, as disclosedby Galli, et al., Angew. Macromol. Chem., Vol. 120, 73 (1984), or by E.P. Moore, et al. in Polypropylene Handbook, Hanser Publishers, New York,1996, particularly pages 11-98. Polypropylene polymers include Shell'sKF 6100 homopolymer polypropylene; Solvay's KS 4005 polypropylenecopolymer; Solvay's KS 300 polypropylene terpolymer; and INSPIRE™polypropylene resins available from The Dow Chemical Company.

Preferably, the propylene-based polymer has a melt flow rate (MFR) inthe range of 0.01 to 1000 g/10 min, more preferably in range of 0.1 to500 g/10 min, and more preferably 1 to 100 g/10 min, as measured inaccordance with ASTM D 1238 at 230° C./2.16 kg.

The propylene-based polymer used in the present invention may be of anymolecular weight distribution (MWD). Propylene-based polymers of broador narrow MWD are formed by means within the skill in the art.Propylene-based polymers having a narrow MWD can be advantageouslyprovided by visbreaking or my manufacturing reactor grades (nonvisbroken) using single-site catalysis, or by both methods.

The propylene-based polymer can be reactor-grade, visbroken, branched orcoupled to provide increased nucleation and crystallization rates. Theterm “coupled” is used herein to refer to propylene-based polymers whichare rheology-modified, such that they exhibit a change in the resistanceof the molten polymer to flow during extrusion (for example, in theextruder immediately prior to the annular die). Whereas “visbroken” isin the direction of chain-scission, “coupled” is in the direction ofcrosslinking or networking. As an example of coupling, a couple agent(for example, an azide compound) is added to a relatively high melt flowrate polypropylene polymer, such that after extrusion, the resultantpolypropylene polymer composition attains a substantially lower meltflow rate than the initial melt flow rate. Preferably, for coupled orbranched polypropylene, the ratio of subsequent MFR to initial MFR isless than, or equal, to 0.7:1, more preferably less than or equal to0.2:1.

A suitable branched propylene-based polymers for use in the presentinvention are commercially available, for instance from Montell NorthAmerica, under the trade designations Profax PF-611 and PF-814.Alternatively, suitable branched or coupled propylene-based polymers canbe prepared by means, within the skill in the art, such as by peroxideor electron-beam treatment, for instance as disclosed by DeNicola et al.in U.S. Pat. No. 5,414,027 (the use of high energy (ionizing) radiationin a reduced oxygen atmosphere); EP 0 190 889 to Himont (electron beamirradiation of isotactic polypropylene at lower temperatures); U.S. Pat.No. 5,464,907 (Akzo Nobel NV); EP 0 754 711 Solvay (peroxide treatment);and U.S. patent application Ser. No. 09/133,576, filed Aug. 13, 1998(azide coupling agents). Each of these patents/applications isincorporated herein by reference.

Suitable propylene/α-olefin interpolymers, comprising at least 50 mol %polymerized propylene, fall within the invention. Suitable polypropylenebase polymers include VERSIFY™ polymers (The Dow Chemical Company) andVISTAMAXX™ polymers (ExxonMobil Chemical Co.), LICOCENE™ polymers(Clariant), EASTOFLEX™ polymers (Eastman Chemical Co.), REXTAC™ polymers(Hunstman), and VESTOPLAST™ polymers (Degussa). Other suitable polymersinclude propylene-α-olefins block copolymers and interpolymers, andother propylene based block copolymers and interpolymers known in theart.

Preferred comonomers include, but are not limited to, ethylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-octene, non-conjugated dienes, polyenes,butadienes, isoprenes, pentadienes, hexadienes (for example,1,4-hexadiene), octadienes, styrene, halo-substituted styrene,alkyl-substituted styrene, tetrafluoroethylenes, vinylbenzocyclobutene,naphthenics, cycloalkenes (for example, cyclopentene, cyclohexene,cyclooctene), and mixtures thereof. Typically and preferably, thecomonomer is an ethylene or a C₄-C₂₀ α-olefin. Preferred comonomersinclude ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene,and more preferably include ethylene, 1-butene, 1-hexene and 1-octene.

In another embodiment, the propylene-based polymer is apropylene/α-olefin interpolymer, which has a molecular weightdistribution less than, or equal to, 5, and preferably less than, orequal to, 4, and more preferably less than, or equal to 3. Morepreferably the propylene/α-olefin interpolymer has a molecular weightdistribution from 1.1 to 5, and more preferably from about 1.5 to 4.5,and more preferably from about 2 to 4. In another embodiment, themolecular weight distribution is less than about 3.5, preferably lessthan about 3.0, more preferably less than about 2.8, more preferablyless than about 2.5, and most preferably less than about 2.3. Allindividual values and subranges from about 1 to 5 are included hereinand disclosed herein.

In another embodiment, the propylene/α-olefin interpolymer has a meltflow rate (MFR) less than, or equal to 1000 g/10 min, preferably lessthan, or equal to 500 g/10 min, and more preferably less than, or equalto 100 g/10 min, and even more preferably less than, or equal to 50 g/10min, as measured in accordance with ASTM D 1238 at 230° C./2.16 kg. Inanother embodiment, propylene/α-olefin interpolymer has a melt flow rate(MFR) greater than, or equal to 0.01 g/10 min, preferably greater than,or equal to 0.1 g/10 min, and more preferably greater than, or equal to1 g/10 min, as measured in accordance with ASTM D 1238 at 230° C./2.16kg.

In another embodiment, the propylene/α-olefin interpolymer has a meltflow rate (MFR) in the range of 0.01 to 1000 grams/10 minutes, morepreferably in range of 0.01 to 500 grams/10 minutes, more preferablyfrom 0.1 to 100 grams/10 min, and even more preferably from 0.1 to 50grams/10 min, as measured in accordance with ASTM D 1238 at 230° C./2.16kg. All individual values and subranges from 0.01 to 1000 grams/10 minare included herein and disclosed herein.

In another embodiment, the propylene/α-olefin interpolymer has a percentcrystallinity of less than, or equal to, 50 percent, preferably lessthan, or equal to, 40 percent, and more preferably less than, or equalto, 35 percent, as measured by DSC. Preferably, these polymers have apercent crystallinity from 2 percent to 50 percent, including allindividual values and subranges from 2 percent to 50 percent. Suchindividual values and subranges are disclosed herein.

In another embodiment, the propylene/α-olefin interpolymer has a densityless than, or equal to, 0.90 g/cc, preferably less than, or equal to,0.89 g/cc, and more preferably less than, or equal to, 0.88 g/cc. Inanother embodiment, the propylene/α-olefin interpolymer has a densitygreater than, or equal to, 0.83 g/cc, preferably greater than, or equalto, 0.84 g/cc, and more preferably greater than, or equal to, 0.85 g/cc.

In another embodiment, the propylene/α-olefin interpolymer has a densityfrom 0.83 g/cm³ to 0.90 g/cm³, and preferably from 0.84 g/cm³ to 0.89g/cm³, and more preferably from 0.85 g/cm³ to 0.88 g/cm³. All individualvalues and subranges from 0.83 g/cm³ to 0.90 g/cm³, are included hereinand disclosed herein.

In another embodiment, the propylene-based polymer is apropylene/ethylene interpolymer, which has a molecular weightdistribution less than, or equal to, 5, and preferably less than, orequal to, 4, and more preferably less than, or equal to 3. Morepreferably the propylene/ethylene interpolymer has a molecular weightdistribution from 1.1 to 5, and more preferably from 1.5 to 4.5, andmore preferably from 2 to 4. In another embodiment, the molecular weightdistribution is less than about 3.5, preferably less than about 3.0,more preferably less than about 2.8, more preferably less than about2.5, and most preferably less than about 2.3. All individual values andsubranges from about 1 to 5 are included herein and disclosed herein.

In another embodiment, the propylene/ethylene interpolymer has a meltflow rate (MFR) less than, or equal to 1000 g/10 min, preferably lessthan, or equal to 500 g/10 min, and more preferably less than, or equalto 100 g/10 min, and even more preferably less than, or equal to 50 g/10min, as measured in accordance with ASTM D 1238 at 230° C./2.16 kg. Inanother embodiment, propylene/ethylene interpolymer has a melt flow rate(MFR) greater than, or equal to 0.01 g/10 min, preferably greater than,or equal to 0.1 g/10 min, and more preferably greater than, or equal to1 g/10 min, as measured in accordance with ASTM D 1238 at 230° C./2.16kg.

In another embodiment, the propylene/ethylene interpolymer has a meltflow rate (MFR) in the range of 0.01 to 1000 grams/10 minutes, morepreferably in range of 0.01 to 500 grams/10 minutes, more preferablyfrom 0.1 to 100 grams/10 min, and even more preferably from 0.1 to 50grams/10 min, as measured in accordance with ASTM D 1238 at 230° C./2.16kg. All individual values and subranges from 0.01 to 1000 grams/10 minare included herein and disclosed herein.

In another embodiment, the propylene/ethylene interpolymer has a percentcrystallinity of less than, or equal to, 50 percent, preferably lessthan, or equal to, 40 percent, and more preferably less than, or equalto, 35 percent, as measured by DSC. Preferably, these polymers have apercent crystallinity from 2 percent to 50 percent, including allindividual values and subranges from 2 percent to 50 percent. Suchindividual values and subranges are disclosed herein.

In another embodiment, the propylene/ethylene interpolymer has a densityless than, or equal to, 0.90 g/cc, preferably less than, or equal to,0.89 g/cc, and more preferably less than, or equal to 0.88 g/cc. Inanother embodiment, the propylene/α-olefin interpolymer has a densitygreater than, or equal to, 0.83 g/cc, preferably greater than, or equalto, 0.84 g/cc, and more preferably greater than, or equal to, 0.85 g/cc.

In another embodiment, the propylene/ethylene interpolymer has a densityfrom 0.83 g/cm³ to 0.90 g/cm³, and preferably from 0.84 g/cm³ to 0.89g/cm³, and more preferably from 0.85 g/cm³ to 0.88 g/cm³. All individualvalues and subranges from 0.83 g/cm³ to 0.90 g/cm³, are included hereinand disclosed herein.

The propylene copolymers of this invention typically comprise unitsderived from propylene in an amount of at least about 60, preferably atleast about 80 and more preferably at least about 85, weight percent ofthe copolymer. The typical amount of units derived from ethylene inpropylene/ethylene copolymers is at least about 0.1, preferably at leastabout 1 and more preferably at least about 5 weight percent, and themaximum amount of units derived from ethylene present in thesecopolymers is typically not in excess of about 35, preferably not inexcess of about 30 and more preferably not in excess of about 20, weightpercent of the copolymer. The amount of units derived from theunsaturated comonomer(s), if present, is typically at least about 0.01,preferably at least about 1 and more preferably at least about 5, weightpercent, and the typical maximum amount of units derived from theunsaturated comonomer(s) typically does not exceed about 35, preferablyit does not exceed about 30 and more preferably it does not exceed about20, weight percent of the copolymer. The combined total of units derivedfrom ethylene and any unsaturated comonomer typically does not exceedabout 40, preferably it does not exceed about 30 and more preferably itdoes not exceed about 20, weight percent of the copolymer.

The copolymers of this invention comprising propylene and one or moreunsaturated comonomers, other than ethylene, also typically compriseunits derived from propylene in an amount of at least about 60,preferably at least about 70 and more preferably at least about 80,weight percent of the copolymer. The one or more unsaturated comonomersof the copolymer comprise at least about 0.1, preferably at least about1 and more preferably at least about 3, weight percent, and the typicalmaximum amount of unsaturated comonomer does not exceed about 40, andpreferably it does not exceed about 30, weight percent of the copolymer.

In a preferred embodiment, these propylene-based polymers are made usinga metal-centered heteroaryl ligand catalyst in combination with one ormore activators, e.g., an alumoxane. In certain embodiments, the metalis one or more of hafnium and zirconium. More specifically, in certainembodiments of the catalyst, the use of a hafnium metal has been foundto be preferred as compared to a zirconium metal for heteroaryl ligandcatalysts. The catalysts in certain embodiments are compositionscomprising the ligand and metal precursor, and, optionally, mayadditionally include an activator, combination of activators oractivator package.

The catalysts used to make the propylene-based polymers additionallyinclude catalysts comprising ancillary ligand-hafnium complexes,ancillary ligand-zirconium complexes and optionally activators, whichcatalyze polymerization and copolymerization reactions, particularlywith monomers that are olefins, diolefins or other unsaturatedcompounds. Zirconium complexes, hafnium complexes, compositions can beused. The metal-ligand complexes may be in a neutral or charged state.The ligand to metal ratio may also vary, the exact ratio being dependenton the nature of the ligand and metal-ligand complex. The metal-ligandcomplex or complexes may take different forms, for example, they may bemonomeric, dimeric, or of an even higher order. Suitable catalyststructures and associated ligands are described in U.S. Pat. No.6,919,407, column 16, line 6 to column 41, line 23, which isincorporated herein by reference. In a further embodiment, thepropylene-based polymer comprises at least 50 weight percent propylene(based on the total amount of polymerizable monomers) and at least 5weight percent ethylene (based on the total amount of polymerizablemonomer), and has ¹³C NMR peaks, corresponding to a region error, atabout 14.6 and 15.7 ppm, and the peaks are of about equal intensity (forexample, see U.S. Pat. No. 6,919,407, column 12, line 64 to column 15,line 51).

The propylene-based polymers can be made by any convenient process. Inone embodiment, the process reagents, i.e., (i) propylene, (ii) ethyleneand/or one or more unsaturated comonomers, (iii) catalyst, and, (iv)optionally, solvent and/or a molecular weight regulator (e.g.,hydrogen), are fed to a single reaction vessel of any suitable design,for example, stirred tank, loop, or fluidized-bed. The process reagentsare contacted within the reaction vessel under appropriate conditions(e.g., solution, slurry, gas phase, suspension, high pressure) to formthe desired polymer, and then the output of the reactor is recovered forpost-reaction processing. All of the output from the reactor can berecovered at one time (as in the case of a single pass or batchreactor), or it can be recovered in the form of a bleed stream, whichforms only a part, typically a minor part, of the reaction mass (as inthe case of a continuous process reactor, in which an output stream isbled from the reactor, at the same rate at which reagents are added tomaintain the polymerization at stead-state conditions). “Reaction mass”means the contents within a reactor, typically during, or subsequent to,polymerization. The reaction mass includes reactants, solvent (if any),catalyst, and products and by-products. The recovered solvent andunreacted monomers can be recycled back to the reaction vessel. Suitablepolymerization conditions are described in U.S. Pat. No. 6,919,407,column 41, line 23 to column 45, line 43, incorporated herein byreference.

Preferably, the functionalized propylene-based polymer, comprising animide functionality, has a melt flow rate (MFR) in the range of 0.01 to1000 g/10 min, more preferably in range of 0.1 to 500 g/10 min, and morepreferably 1 to 100 g/10 min, as measured in accordance with ASTM D 1238at 230° C./2.16 kg.

Additional Reactions and/or Blends

The amine functionalized olefin multiblock interpolymer or hydroxylfunctionalized olefin multiblock interpolymer, each according to theinvention, may be reacted or blended with a second polymer by meltreaction, for example, in a Brabender mixer or an extruder. This may beconducted in the same reactor as the functionalization reaction, orsubsequently, in another melt reactor. The reaction time and temperaturewill depend on the polymers present. Thus, for example, aminofunctionalized polypropylene (amino-PP) may be melt reacted/blended witha blend of styrene-maleic acid polymer in polypropylene.

Similarly, polyolefin blends comprising a polyolefin, an aminatedpolyolefin and other polymer, such as an engineering thermoplastic thatis reactive with, or otherwise compatible with, the aminated olefinmultiblock interpolymer, can be prepared having improved overall blendcompatibility between the polyolefin, other polymer, and aminated olefinmultiblock interpolymer. In addition, the functionalized olefinmultiblock interpolymers or blends can be blended with one or morethermoplastic or thermosetting polymers, and used in other applications.

Thermoplastic polymers include the natural or synthetic resins, such as,for example, styrene block copolymers, rubbers, linear low densitypolyethylene (LLDPE), high density polyethylene (HDPE), low densitypolyethylene (LDPE), ethylene/vinyl acetate (EVA) copolymer,ethylene-carboxylic acid copolymers (EAA), ethylene acrylate copolymers,polybutylene, polybutadiene, nylons, polycarbonates, polyesters,polypropylene, ethylene-propylene interpolymers such asethylene-propylene rubber, ethylene-propylene-diene monomer rubbers,chlorinated polyethylene, thermoplastic vulcanates, ethyleneethylacrylate polymers (EEA), ethylene styrene interpolymers (ESI),polyurethanes, as well as graft-modified olefin polymers, andcombinations of two or more of these polymers.

The blend compositions of the present invention can be used in a varietyof applications including thermoforming, blow molding, injection moldingand overmolding, calendering, fiber forming processes, wire and cable,extrusion coatings and dispersions.

Processing aids, such as plasticizers, can also be included in eitherthe individual blend components or added to the final blend. Theseinclude, but are not limited to, the phthalates, such as dioctylphthalate and diisobutyl phthalate, natural oils such as lanolin, andparaffin, naphthenic and aromatic oils obtained from petroleum refining,and liquid resins from rosin or petroleum feedstocks. Exemplary classesof oils useful as processing aids include white mineral oil such asKaydol™ oil (available from and a registered trademark of Witco) andShellflex™ 371 naphthenic oil (available from and a registered trademarkof Shell Oil Company). Another suitable oil is Tuflo™ oil (availablefrom and a registered trademark of Lyondell).

Additives

Typically polymers and resins used in the invention are treated with oneor more stabilizers, for example, antioxidants, such as Irganox™ 1010and Irgafos™ 168, both supplied by Ciba Specialty Chemicals. Polymersare typically treated with one or more stabilizers before an extrusionor other melt processes. Other polymeric additives include, but are notlimited to, ultraviolet light absorbers, antistatic agents, pigments,dyes, nucleating agents, fillers slip agents, fire retardants,plasticizers, processing aids, lubricants, stabilizers, smokeinhibitors, viscosity control agents and anti-blocking agents.

Applications

The functionalized olefin multiblock interpolymers of the invention canbe used in various applications, including, but not limited to adhesivesto polymer substrates and foams, for example adhesives to polyurethanefilms and foams, and adhesives to polyesters; dyes, paint adhesives andpaint adhesion enablers; weldability applications; automotive interiorsand exteriors; lubricants and engine oil components; fibers; fabrics;compatibilizers for polymer compositions; toughening agents for polymercompositions; conveyor belts; films; adhesives; footwear components;artificial leather; injection molded objects, such as injection moldedtoys; roofing and construction materials; dispersions; carpetcomponents, such as carpet backings; and artificial turf.

In particular, the inventive functionalized olefin multiblockinterpolymers can be used in the following applications: (a) outsoles,midsoles and stiffners, to be assembled with standard polyurethaneadhesive systems currently used by footwear industry, (b) painting ofsoles and mid-soles with polyurethane paints, currently used by footwearindustry, and (c) over-molding of olefin multiblock interpolymers andbi-component polyurethanes for multilayered soles and midsoles. Inaddition, polyolefin/polyurethane blends can be used in otherapplications, such as automotive applications and constructionapplications. Automotive applications include, but are not limited to,the manufacture of bumper fascias, vertical panels, soft TPO skins,interior trim. Construction applications include, but are not limitedto, the manufacture of furniture and toys.

Additional applications include adhesion of co-extruded films, where oneor more substrates are compatible or reactive with hydroxyl groups, andthe lamination of polyolefin based films to other polar substrates (forexample, glass lamination). Further applications include artificialleather to be adhered to polar substrates, such as polyurethane,polyvinyl chloride (PVC), and others. Artificial leather is used forautomotive interiors adhering to polyurethane for seating, head liners.

The functionalized olefin multiblock interpolymers are also suitable forHealth & Hygiene products, such as wipes, cleaning tissues, foams ordirectly dyable fibers. The functionalized olefin multiblockinterpolymers can be used to enhance hydrophilicity of the elastomer fornovel membrane structures for separation of breathability. Thefunctionalized olefin multiblock interpolymers are also suitable for useas self-adhearable elastomers onto metal or textile structures forautomotive. As discussed above, the functionalized olefin multiblockinterpolymers are well suited for blends and compatibilizers withenhanced interaction towards polar polymers, such as TPU, EVA, PVC, PC,PET, PLA (polylactic acid), polyamide esters, and PBT. Such bends can beused for novel compounds for footwear, automotive, consumer, durables,appliances, electronic housing, apparel, and conveyor belts. Thefunctionalized olefin multiblock interpolymers can also serve ascompatibilizers between natural fibers and other polyolefins for use inapplications, such as wood binding formulations or cellulose bindingformulations. The functionalized olefin multiblock interpolymers of theinvention are also useful in blends with one or more polyether blockamides, such as Pebax® polymers available from Arkema. Thefunctionalized olefin multiblock interpolymers may also be used asimpact modifiers for nylon. In addition, amine groups of the inventivefunctionalized olefin multiblock interpolymers may be protonated oralkylated to form quartnary nitrogens or ionomers for use asanti-microbials.

The functionalized olefin multiblock interpolymers can also be used toenhance the interaction to fillers, such as silica, carbon black orclay, for use in formulations for toners, tires, coatings or othercompounds. The functionalized olefin multiblock interpolymers may alsobe used in engine oil viscosity modifiers, engine oil dispersants,dyable or printable fibers for apparel, paint adhesion promoters,adhesives for glass, metal and PVDC barrier resins, dispersions,components in primers and sizing agents.

Thus the invention also provides a painted substrate, the substrateformed from an inventive composition as described herein, and the paintcomprising at least one of an acrylic polymer, alkyd resin,cellulose-based material, melamine resin, urethane resin, carbamateresin, polyester resin, vinyl acetate resin, polyol and alcohols. In afurther embodiment, the paint is a water-based. In another embodiment,the paint is an organic solvent based.

This embodiment of the invention works well with a wide variety of paintformulations. The major components of solvent-borne paints and coatingsare solvents, binders, pigments, and additives. In paint, thecombination of the binder and solvent is referred to as the paintvehicle. Pigment and additives are dispersed within the vehicle. Theamount of each constituent varies with the particular paint, butsolvents traditionally make up about 60 percent of the totalformulation. Typical solvents include toluene, xylene, methyl ethylketone, methyl isobutyl ketone and water. Binders account for about 30weight percent, pigments for 7 to 8 weight percent, and additives for 2to 3 weight percent. Some of the polymers and other additives used inpaint formulations include: acrylic polymers, alkyd resins, cellulosebased materials, such as cellulose acetate butyrate, melamine resins,carbamate resins, polyester resins, vinyl acetate resins, urethaneresins, polyols, alcohols, inorganic materials such as titanium dioxide(rutile), mica flakes, iron oxide, silica, aluminum, and the like.

The invention also provides an over-molded article, the article formedfrom a polar substrate and a molded overlay formed from an inventivecomposition, as described herein.

In another embodiment, the invention provides an over-molded article,the article formed from a substrate comprising an inventive composition,as described herein, and a molded overlay comprising a polar material.In further embodiment, the article is in the form of a grip, handle orbelt.

The invention also provides a laminated structure comprising a firstlayer and a second layer, the first layer formed from an inventivecomposition, as described herein, and the second layer formed from acomposition comprising a polar material. In a further embodiment, one ofthe layers is in the form of a foam. In another embodiment, one of thelayers is in the form of a fabric. In a further embodiment, thelaminated structure is in the form of an awning, tarp or automobile skinor steering wheel.

The invention also provides a molded article comprising a firstcomponent and a second component, the first component is formed from apolar material, and the second component formed from an inventivecomposition, as described herein. In a further embodiment, the articleis in the form of an automobile skin, appliqué, footwear, conveyor belt,timing belt or consumer durable.

The invention also provides an article comprising at least one componentformed from an inventive composition, as described herein. In a furtherembodiment, the article is a carpet, an adhesive a wire sheath, a cable,a protective apparel, a coating or a foam laminate. In anotherembodiment, the article is a tie layer between extruded sheets, films orprofiles; a tie layer between cast sheets, films or profiles; anautomotive skin; and awning; a tarp; a roofing construction article (forexample, adhesives to epoxy, urethane or acrylic-based substrates forall roofing applications, such as insulating bonding, liquid roofing,façade sealant, expansion joints, wet-room sealants, pitched roof,acrylics-adhered roof, bitumen bonding, and PUR-adhered refurbishment);a steering wheel; a powder coating; a powder slush molding; a consumerdurable; a grip; a handle; a computer component; a belt; an appliqués, afootwear component, adhesive a conveyor or timing belt, or a fabric.

“Laminates”, “laminations” and like terms mean two or more layers, forexample, film layers, in intimate contact with one another. Laminatesinclude molded articles bearing a coating. Laminates are not blends,although one or more layers of a laminate may comprise a blend.

“Polar”, “polar polymer” and like terms mean that the polymer moleculeshave a permanent dipole, i.e., the polymer molecule has a positive endand a negative end. In other words, the electrons in a polar moleculeare not shared equally among the atoms of the molecule. In contrast,“nonpolar”, “nonpolar polymer” and like terms mean that the polymermolecules do not have a permanent dipole, i.e., the polymer does nothave a positive end and a negative end. The electrons in a nonpolarmolecule are essentially equally shared among the atoms of the molecule.Most hydrocarbon liquids and polymers are nonpolar.

Polymers substituted with carboxyl, hydroxyl and the like are oftenpolar polymers. Articles prepared from nonpolar polymers have relativelylow surface energy, that is, less than about 32 dyne per centimeter(dyne/cm), and articles prepared from polar polymers have relativelyhigh surface energy, that is, 32 or more dyne/cm. The nonpolar materialof this invention typically comprises one or more nonpolar thermoplasticolefinic polymers, typically elastomers, free of any significant amountof polar functionality, for example, hydroxyl, carboxyl, carbonyl,ester, ether, amide, mercaptan, halide and the like groups. The polarmaterial of this invention typically comprises one or more polymerscomprising one or more polar functionalities. Typical polymerscomprising one more polar functionalities include, but are not limitedto, polyesters, polyethers, polylactic acid, polycarbonates, nylons,polysulfides, polysulfones, polyurethanes, polyvinyl alcohol, poly(vinylacetate), poly(vinyl chloride), acrylonitrile, ABS, polyamide esters,and polysiloxanes.

“Insignificant amount of polar functionality,” and like terms, mean thata polymer does not comprise a sufficient number of polar functionalgroups to impart a surface energy of at least about 32 dyne/cm to anarticle made from it.

“Over-molding,” and like terms, refer to a process in which one resin isinjection into a mold comprising a pre-placed substrate, and molded overthis substrate. Over-molding is typically used to improve theperformance and properties of a final product by over-molding one resinover another polymer substrate. Over-molding can be used to formseamless, integrated parts. Examples of over-molded parts includeflexible grip handles on power tools and kitchen utensils, which provideadditional gripping properties, without the hygienic concern normallyassociated with mechanical assemblies. The substrate may be any suitablematerial, such as a plastic, metal or ceramic part.

“Molded overlay,” and like terms, refer to an article comprising atleast two parts (an injection molded part and a substrate) that arebound together. The injection molded part is placed on top of thesubstrate, outside the injection mold. An adhesive may be used to bindthe injection molded part to the substrate. The substrate may be anysuitable material, such as a plastic, metal or ceramic part.

The substrates to which the inventive functionalized olefin multiblockinterpolymers, and compositions comprising the same, can be applied,include a wide range of materials, both polar and nonpolar, such as butnot limited to, polymers, metal, wood, concrete, glass, ceramic, andvarious composites of two or more of these materials. Alternatively,these materials can be applied to an article formed from an inventivefunctionalized olefin multiblock interpolymers, and compositionscomprising the same.

Application methods include painting, printing, dying, over-molding andthe like, including the many variations on each, for example, spreading,spraying, dipping, extrusion, and other processes. The functionalizedolefin multiblock interpolymers, and compositions comprising the same,can be crosslinked before, during or after application to a substrate,and they can be crosslinked in any convenient manner, for example,peroxide, sulfur, moisture, silane, radiation, heat and the like. In oneembodiment, the functionalized olefin multiblock interpolymers, andcompositions comprising the same, is applied to a substrate, and thefunctionalized olefin multiblock interpolymers is crosslinked, as it isapplied, and/or after it is applied. For crosslinking, thefunctionalized olefin multiblock interpolymers will usually containunsaturation, e.g., a diene-containing PO.

In one embodiment, the inventive functionalized olefin multiblockinterpolymers, and compositions comprising the same, can be used to forma tie layer between polar and nonpolar materials, particularly betweenpolar and nonpolar polymeric materials, for example, between a filmlayer of a nonpolar-PO, such as polyethylene or polypropylene, and afilm layer of a polar polymer such as polylactic acid (PLA) or polyamideor polyester. The functionalized olefin multiblock interpolymers of thisinvention are particularly well suited as tie layers for bindingtogether a) a polyethylene or polypropylene film, or a polyethylene orpolypropylene surface of a molded article, to b) a film, or surface of amolded article, of an ethylene/acrylic acid copolymer (EAA) or acopolymer of PLA or polyethylene terephthalate (PET). Any processes thatcombine co-extrusion, extrusion lamination, adhesive lamination, and/orfoam casting or extrusion can be used to create these laminatedstructures, including structures in which one layer comprises a foam.

In another embodiment, the invention provides a laminate structurecomprising a polycarbonate, as the base sheet having variable thickness,and preferably having at least one textured surface on which afunctionalized olefin multiblock interpolymer of the invention can beadhered, typically by a compression molding process at moderatetemperatures of 140° C. Such laminates have been shown to have excellentadhesion; for example a peel strength of 1N/mm in the case of an olefinmultiblock interpolymer functionalized with secondary amine groups at aconcentration of 1.1 weight percent. This article can be furtherlaminated with polyolefin using conventional welding techniques, forexample, by pressure and heat. In addition, a second polycarbonate sheetwith a textured surface interfacing the functionalized olefin multiblockinterpolymer film can be laminated over the functionalized olefinmultiblock interpolymer.

In another embodiment, the invention provides an over molded articlecomprising a polycarbonate, as the base sheet having variable thickness,and preferably having at least textured face on which functionalizedolefin multiblock interpolymer can be adhered, typically by acompression molding process, at a moderate temperatures of 140° C. Sucharticles have excellent adhesion. This article can be further laminatedwith polyolefin using conventional welding techniques, such as bypressure and heat, or a second polycarbonate sheet with a texturedsurface can be adhered to the exposed surface of the functionalizedolefin multiblock interpolymer film.

Another embodiment of this invention as a multi-laminate structure ofpolycarbonate and polyolefin films, intercalated for increased toughnessof the final structure. Another embodiment would be a functionalizedolefin multiblock interpolymer elastomeric coating deposited on thesurface of polycarbonate to provide a scratch resistant assembly coatthat could be easily thermoformed, for example at a thermoformingtemperature of 160° C.

The invention also provides a footwear article comprising at least onecomponent formed from a composition comprising a functionalized olefinmultiblock interpolymer. In one embodiment, the article is selected fromthe group consisting of shoe outsole, shoe midsole, shoe unitsole, anovermolded article, a natural leather article, a synthetic leatherarticle, an upper, a laminated article, a coated article, a boot, asandal, galoshes, a plastic shoe, and combinations thereof.

The functionalized olefin multiblock interpolymers may also be use indispersions, including, but not limited to, water-based dispersions foruse as primers in olefinic footwear that promote adhesion to PU gluesand leather; fabric coating adhesion (adhesion to PET, Nylon, PP,elastomer rich TPO comprising of POE, EPDM or other non-polar elastomersor combination thereof etc.).

DEFINITIONS

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least two units between any lower value and anyhigher value. As an example, if it is stated that a compositional,physical or mechanical property, such as, for example, molecular weight,viscosity, melt index, etc., is from 100 to 1,000, it is intended thatall individual values, such as 100, 101, 102, etc., and sub ranges, suchas 100 to 144, 155 to 170, 197 to 200, etc., are expressly enumerated inthis specification. For ranges containing values which are less thanone, or containing fractional numbers greater than one (for example,1.1, 1.5, etc.), one unit is considered to be 0.0001, 0.001, 0.01 or0.1, as appropriate. For ranges containing numbers less than ten (forexample, 1 to 5), one unit is typically considered to be 0.1. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. Numerical ranges have been recited, as discussedherein, in reference to melt index, molecular weight distribution,percent crystallinity, density and other properties.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The terms “blend” or “polymer blend,” or “mixture” as used herein, meana blend of two or more polymers. Such a blend may or may not be miscible(not phase separated at molecular level). Such a blend may or may not bephase separated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin interpolymers do notinclude those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefininterpolymers can be blended with one or more polymers, the as-producedethylene/α-olefin interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises more than 50 mole percent polymerized ethylene monomer(based on the total amount of polymerizable monomers), and optionallymay contain at least one comonomer. These are not typically referred toas olefin multiblock polymers.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises more than 50 mole percent polymerized propylene monomer(based on the total amount of polymerizable monomers), and optionallymay contain at least one comonomer. These are not typically referred toas olefin multiblock polymers.

The term, “propylene/α-olefin interpolymer,” as used herein, refers toan interpolymer that contains more than 50 mole percent polymerizedpropylene monomer (based on the total amount of polymerizable monomers),and at least one α-olefin.

The term, “propylene/ethylene interpolymer,” as used herein, refers toan interpolymer that comprises more than 50 mole percent polymerizedpropylene monomer (based on the total amount of polymerizable monomers),ethylene monomer, and, optionally, at least one α-olefin.

The term “amine-reactive group,” as used herein, refers to a chemicalgroup or chemical moiety that can react with an amine group.

The term “hydroxy-reactive group,” or “hydroxy-reactive group,” as usedherein, refers to a chemical group or chemical moiety that can reactwith a hydroxy group.

The term “imbibing,” and similar terms, as used herein, refers to theprocess in which a compound is absorbed into a polymer solid, particle,pellet, or article.

The term “nonpolar” polymer, as used herein, refers to a polymer thatdoes not contain polar moieties, including, but not limited to, hydroxylgroup, carbonyl group, ester group, amine group, amino group, amidegroup, imide group, cyano group, thiol group, and carboylic acid group.Examples of nonpolar polymers include polyolefin polymers.

The term “polar” polymer, as used herein, refers to a polymer thatcontains one or more polar moieties, including, but not limited to,hydroxyl group, carbonyl group, ester group, amine group, amino group,amide group, imide group, cyano group, thiol group, and carboylic acidgroup. Examples of polar polymers include polyesters, polyamides,polyimides, polyacrylic acids, polyethers, polyether block amides,polyetheramides, polyetherimides, polycarbonates, polyphenyleneoxides,polyvinylalcohols, polylactic acids, polyamide esters andpolyvinylchlorides.

Testing Methods

In examples 1-21, the following analytical techniques are employed:

GPC Method for Samples 1-4 and A-D

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm Ionolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400-600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 25 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./minheating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431 (M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a holt press under the following conditions: zero pressure for 3min at 190° C., followed by 86 MPa for 2 min at 190° C., followed bycooling inside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:

${\%\mspace{14mu}{Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:

${\%\mspace{14mu}{Stress}\mspace{14mu}{Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting of softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixture reaches 65 mm.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg for polyethylene-based polymers (Condition 230° C./2.16kg for polypropylene-based polymers). Melt index, or I₁₀ is alsosometimes measured in accordance with ASTM D 1238, Condition 190° C./10kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macomol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec². The required tensile force is recorded as afunction of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

The preparation of catalyst (B1) is conducted as follows.

a) Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,983, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA12), n-octylaluminumdi(ethyl(1-naphthyl)amide (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA16), n-octylaluminumbis(2,2,6,7-dibenzo-1-azacycloheptaneamide) (SA17), n-octylaluminumbis(dimethyl(t-butyl)siloxide (SA18), ethylzinc (2,6-diphenylphenoxide)(SA19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4, Comparative A-C General High Throughput ParallelPolymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx technologies, Inc.,and operated substantially according to U.S. Pat. Nos. 6,248,540,6,030,917, 6,362,309, 6,306,658, and 6,316,663. Ethylenecopolymerizations are conducted at 130° C. and 200 psi (1.4 MPa) withethylene on demand using 1.2 equivalents of cocatalyst 1 based on totalcatalyst used (1.1 equivalents when MMAO is present). A series ofpolymerizations are conducted in a parallel pressure reactor (PPR)contained of 48 individual reactor cells in a 6×8 array that are fittedwith a pre-weighed glass tube. The working volume in each reactor cellis 6000 μL. Each cell is temperature and pressure controlled withstirring provided by individual stirring paddles. The monomer gas andquench gas are plumbed directly into the PPR unit and controlled byautomatic valves. Liquid reagents are robotically added to each reactorcell by syringes and the reservoir solvent is mixed alkanes. The orderof addition is mixed alkanes solvent (4 ml), ethylene, 1-octenecomonomer (1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttlingagent, and catalyst or catalyst mixture. When a mixture of cocatalyst 1and MMAO or a mixture of two catalysts is used, the reagents arepremixed in a small vial immediately prior to addition to the reactor.When a reagent is omitted in an experiment, the above order of additionis otherwise maintained. Polymerizations are conducted for approximately1-2 minutes, until predetermined ethylene consumptions are reached.After quenching with CO, the reactors are cooled and the glass tubes areunloaded. The tubes are transferred to a centrifuge/vacuum drying unit,and dried for 12 hours at 60° C. The tubes containing dried polymer areweighed and the difference between this weight and the tare weight givesthe net yield of polymer. Results are contained in Table 1. In Table 1and elsewhere in the application, comparative compounds are indicated byan asterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers of the invention aredistinguishable based on branching or density.

TABLE 1 Cat. (A1) Cat (B1) Cocat MMAO shuttling agent Yield Ex. (μmol)(μmol) (μmol) (μmol) (μmol) (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 —0.1363 300502 3.32 — B* — 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.060.1 0.176 0.8 — 0.2038 45526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0)0.1974 28715 1.19 4.8 2 0.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.1214.4 3 0.06 0.1 0.192 — TEA (8.0) 0.208 22675 1.71 4.6 4 0.06 0.1 0.192— TEA (80.0) 0.1879 3338 1.54 9.4 ¹C₆ or higher chain content per 1000carbons ²Bimodal molecular weight distribution

It may be seen the polymers produced according to the invention have arelatively narrow polydispersity (Mw/Mn) and larger block-copolymercontent (trimer, tetramer, or larger) than polymers prepared in theabsence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for comparative A shows a 90.0° C. melting point (Tm) witha heat of fusion of 86.7 J/g. The corresponding CRYSTAF curve shows thetallest peak at 48.5° C. with a peak area of 29.4 percent. Both of thesevalues are consistent with a resin that is low in density. Thedifference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for comparative B shows a 129.8° C. melting point (Tm)with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for comparative C shows a 125.3° C. melting point (Tm)with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19, Comparatives D-F, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3.

TABLE 2 Process details for preparation of exemplary polymers Cat Cat A1Cat B2 DEZ DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ Flow ConcFlow Conc. Flow [C₂H₄]/ Rate⁵ Conv Solids Ex. kg/hr kg/hr sccm¹ ° C. ppmkg/hr ppm kg/hr % kg/hr ppm kg/hr [DEZ]⁴ kg/hr %⁶ % Eff.⁷ D* 1.63 12.729.90 120 142.2  0.14 — — 0.19 0.32  820 0.17 536 1.81 88.8 11.2 95.2 E*″ 9.5 5.00 ″ — — 109 0.10 0.19 ″ 1743 0.40 485 1.47 89.9 11.3 126.8 F* ″11.3 251.6 ″ 71.7 0.06 30.8 0.06 — — ″ 0.11 — 1.55 88.5 10.3 257.7 5 ″ ″— ″ ″ 0.14 30.8 0.13 0.17 0.43 ″ 0.26 419 1.64 89.6 11.1 118.3 6 ″ ″4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″ 0.18 570 1.65 89.3 11.1 172.7 7 ″ ″21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25 ″ 0.13 718 1.60 89.2 10.6 244.1 8 ″ ″36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.12 1778  1.62 90.0 10.8 261.1 9 ″ ″ 78.43″ ″ ″ ″ ″ ″ 0.04 ″ ″ 4596  1.63 90.2 10.8 267.9 10 ″ ″ 0.00 123 71.10.12 30.3 0.14 0.34 0.19 1743 0.08 415 1.67 90.31 11.1 131.1 11 ″ ″ ″120 71.1 0.16 ″ 0.17 0.80 0.15 1743 0.10 249 1.68 89.56 11.1 100.6 12 ″″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.09 1743 0.07 396 1.70 90.02 11.3 137.0 13 ″″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.05 1743 0.05 653 1.69 89.64 11.2 161.9 14 ″″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.10 1743 0.10 395 1.41 89.42 9.3 114.1 152.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 1743 0.09 282 1.80 89.33 11.3 121.316 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.07 1743 0.07 485 1.78 90.11 11.2 159.717 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.08 1743 ″ 506 1.75 89.08 11.0 155.6 180.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.11 1743 0.10 331 1.25 89.93 8.8 90.2 190.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.09 1743 0.08 367 1.16 90.74 8.4 106.0*Comparative, not an example of the invention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl ⁴molar ratio in reactor ⁵polymer production rate ⁶percentethylene conversion in reactor ⁷efficiency, kg polymer/g M where g M = gHf + g Zr

TABLE 3 Properties of exemplary polymers Heat of Tm − CRYSTAF Density MwMn Fusion T_(m) T_(c) T_(CRYSTAF) T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.)(percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E*0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.912.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20 5 0.8786 1.5 9.8 6.7104,600 53,200 2.0 55 120 101 48 72 60 6 0.8785 1.1 7.5 6.5 109600 533002.1 55 115 94 44 71 63 7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69 121103 49 72 29 8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 80 43 139 0.8836 1.1 9.7 9.1 129600 28,700 4.5 74 125 109 81 44 16 10 0.8784 1.27.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.1 59.2 6.566,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4 101,50055,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,100 63,600 2.142 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9 123 121 10673 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 91 32 82 10 160.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 17 0.8757 1.711.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.1 24.9 6.172,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.0 76,80039,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peat at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer for example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of comparative D shows a peak with a 37.3°C. melting point (Tm) with a heat of fusion of 31.6 J/g. Thecorresponding CRYSTAF curve shows no peak equal to and above 30° C. Bothof these values are consistent with a resin that is low in density. Thedelta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of comparative E shows a peak with a124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.3° C. with apeak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of comparative F shows a peak with a124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 77.6° C. with apeak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidence by TMA temperaturetesting, pellet block strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative G* is substantially linear ethylene/1-octenecopolymer (AFFINITY®, available from The Dow Chemical Company),Comparative H* is an elastomeric, substantially linear ethylene-1-octenecopolymer (AFFINITY® EG8100, available from The Dow Chemical Company),Comparative I is a substantially linear ethylene/1-octene copolymer(AFFINITY® 1840, available from The Dow Chemical Company), Comparative Jis a hydrogenated styrene/butadiene/styrene triblock copolymer (KRATON™G1652, available from KRATON Polymers), Comparative K is a thermoplasticvulcanizate TPV, a polyolefin blend containing dispersed therein acrosslinked elastomer). Results are presented in Table 4.

TABLE 4 High Temperature Mechanical Properties Pellet Blocking 300%Strain TMA-1 mm Strength Recovery Compression penetration lb/ft² G′(25°C.)/ (80° C.) Set (70° C.) Ex. (° C.) (kPa) G′(100° C.) (percent)(percent) D* 51 — 9 Failed — E* 130 — 18 — — F* 70 141 (6.8)  9 Failed100  5 104 0 (0)  6 81 49  6 110 — 5 — 52  7 113 — 4 84 43  8 111 — 4Failed 41  9 97 — 4 — 66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 7913 95 — 6 84 71 14 125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108 0(0)  4 82 47 18 125 — 10 — — 19 133 — 9 — — G* 75 463 (22.2) 89 Failed100 H* 70 213 (10.2) 29 Failed 100 I* 111 — 11 — — J* 107 — 5 Failed 100K* 152 — 3 — 40

In Table 4, Comparative F (which is a physical blend of the two polymersresulting from simultaneous polymerizations using catalyst A1 and B1)has a 1 mm penetration temperature of about 70° C., while Examples 5-9have a 1 mm penetration temperature of 100° C. or greater. Further,examples 10-19 all have a 1 mm penetration temperature of greater than85° C., with most having 1 mm TMA temperature of greater than 90° C. oreven greater than 100° C. This shows that the novel polymers have betterdimensional stability at higher temperatures compared to a physicalblend. Comparative J (a commercial SEBS) has a good 1 mm TMA temperatureof about 107° C., but it has very poor (high temperature 70° C.)compression set of about 100 percent and it also failed to recover(sample broke) during a high temperature (80° C.) 300 percent strainrecovery. Thus the exemplified polymers have a unique combination ofproperties unavailable even in some commercially available, highperformance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative F) has a storage modulus ratio of 9 and arandom ethylene/octene copolymer (Comparative G) of similar density hasa storage modulus ratio an order of magnitude greater (89). It isdesirable that the storage modulus ratio of a polymer be as close to 1as possible. Such polymers will be relatively unaffected by temperature,and fabricated articles made from such polymers can be usefully employedover a broad temperature range. This feature of low storage modulusratio and temperature independence is particularly useful in elastomerapplications such as in pressure sensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers of the inventionpossess improved pellet blocking strength. In particular, Example 5 hasa pellet blocking strength of 0 MPa, meaning it is free flowing underthe conditions tested, compared to Comparatives F and G which showconsiderable blocking. Blocking strength is important since bulkshipment of polymers having large blocking strengths can result inproduct clumping or sticking together upon storage or shipping,resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparatives F, G, H and J all have a 70° C. compression setof 100 percent (the maximum possible value, indicating no recovery).Good high temperature compression set (low numerical values) isespecially needed for applications such as gaskets, window profiles,o-rings, and the like.

TABLE 5 Ambient Temperature Mechanical Properties Tensile 100% 300%Retractive Compres- Stress Flex Elonga- Elonga- Abrasion: Notched StrainStrain Stress sion Relaxa- Modu- Tensile Tensile tion Tensile tionVolume Tear Recovery Recovery at 150% Set tion lus Modulus Strength atBreak¹ Strength at Break Loss Strength 21° C. 21° C. Strain 21° C. at50% Ex. (MPa) (MPa) (MPa)¹ (%) (MPa) (%) (mm³) (mJ) (percent) (percent)(kPa) (Percent) Strain² D* 12 5 — — 10 1074 — — 91 83 760 — — E* 895 589— 31 1029 — — — — — — — F* 57 46 — — 12 824 93 339 78 65 400 42 — 5 3024 14 951 16 1116 48 — 87 74 790 14 33 6 33 29 — — 14 938 — — — 75 86113 — 7 44 37 15 846 14 854 39 — 82 73 810 20 — 8 41 35 13 785 14 810 45461 82 74 760 22 — 9 43 38 — — 12 823 — — — — — 25 — 10 23 23 — — 14 902— — 86 75 860 12 — 11 30 26 — — 16 1090 — 976 89 66 510 14 30 12 20 1712 961 13 931 — 1247  91 75 700 17 — 13 16 14 — — 13 814 — 691 91 — — 21— 14 212 160 — — 29 857 — — — — — — — 15 18 14 12 1127  10 1573 — 2074 89 83 770 14 — 16 23 20 — — 12 968 — — 88 83 1040  13 — 17 20 18 — — 131252 — 1274  13 83 920  4 — 18 323 239 — — 30 808 — — — — — — — 19 706483 — — 36 871 — — — — — — — G* 15 15 — — 17 1000 — 746 86 53 110 27 50H* 16 15 — — 15 829 — 569 87 60 380 23 — I* 210 147 — — 29 697 — — — — —— — J* — — — — 32 609 — — 93 96 1900  25 — K* — — — — — — — — — — — 30 —¹Tested at 51 cm/minute ²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers of the invention have betterretractive stress at 150 percent strain (demonstrated by higherretractive stress values) than some of the comparative samples.Comparative Examples F, G and H have retractive stress value at 150percent strain of 400 kPa or less, while the inventive polymers haveretractive stress values at 150 percent strain of 500 kPa (Ex. 11) to ashigh as about 1100 kPa (Ex. 17). Polymers having higher than 150 percentretractive stress values would be quite useful for elastic applications,such as elastic fibers and fabrics, especially nonwoven fabrics. Otherapplications include diaper, hygiene, and medical garment waistbandapplications, such as tabs and elastic bands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative G. Lower stress relaxation means that the polymer retainsits force better in applications such as diapers and other garmentswhere retention of elastic properties over long time periods at bodytemperatures is desired.

Optical Testing

TABLE 6 Polymer Optical Properties Ex. Internal Haze (percent) Clarity(percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56  5 13 72 60  6 3369 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 67 11 13 69 67 12 875 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 6122 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films substantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multiblock Copolymers

Extraction studies of the polymers of examples 5, 7 and Comparative Eare conducted. In the experiments, the polymer sample is weighed into aglass fritted extraction thimble and fitted into a Kumagawa typeextractor. The extractor with sample is purged with nitrogen, and a 500mL round bottom flask is charged with 350 mL of diethyl ether. The flaskis then fitted to the extractor. The ether is heated while beingstirred. Time is noted when the ether begins to condense into thethimble, and the extraction is allowed to proceed under nitrogen for 24hours. At this time, heating is stopped and the solution is allowed tocool. Any ether remaining in the extractor is returned to the flask. Theether in the flask is evaporated under vacuum at ambient temperature,and the resulting solids are purged dry with nitrogen. Any residue istransferred to a weighed bottle using successive washes of hexane. Thecombined hexane washes are then evaporated with another nitrogen purge,and the residue dried under vacuum overnight at 40° C. Any remainingether in the extractor is purged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7.

TABLE 7 ether ether C₈ hexane hexane C₈ residue wt. soluble soluble molesoluble soluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g)(percent) percent¹ percent¹ Comp. F* 1.097 0.063 5.69 12.2 0.245 22.3513.6 6.5 Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.0171.59 13.3 0.012 1.10 11.7 9.9 ¹Determined by ¹³C NMR

Additional Polymer Examples 19 A-J, Continuous Solution Polymerization,Catalyst A1/B2+DEZ For Examples 19A-I

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from Exxon Mobil, Inc.), ethylene, 1-octene, and hydrogen(where used) are combined and fed to a 27 gallon reactor. The feeds tothe reactor are measured by mass-flow controllers. The temperature ofthe feed stream is controlled by use of a glycol cooled heat exchangerbefore entering the reactor. The catalyst component solutions aremetered using pumps and mass flow meters. The reactor is run liquid-fullat approximately 550 psig pressure. Upon exiting the reactor, water andadditive are injected in the polymer solution. The water hydrolyzes thecatalysts, and terminates the polymerization reactions. The post reactorsolution is then heated in preparation for a two-stage devolatization.The solvent and unreacted monomers are removed during the devolatizationprocess. The polymer melt is pumped to a die for underwater pelletcutting.

For Example 19J

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer.

Process details and results are contained in Table 8. Selected polymerproperties are provided in Tables 9A-C.

In Table 9B, inventive examples 19F and 19G show low immediate set ofaround 65-70% strain after 500% elongation.

TABLE 8 Polymerization Conditions Cat A1² Cat A1 Cat B2³ Cat B2 DEZ C₂H₄C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc Ex. lb/hr lb/hr lb/hr sccm¹° C. ppm lb/hr ppm lb/hr wt% 19A 55.29 32.03 323.03 101 120 600 0.25 2000.42 3.0 19B 53.95 28.96 325.3 577 120 600 0.25 200 0.55 3.0 19C 55.5330.97 324.37 550 120 600 0.216 200 0.609 3.0 19D 54.83 30.58 326.33 60120 600 0.22 200 0.63 3.0 19E 54.95 31.73 326.75 251 120 600 0.21 2000.61 3.0 19F 50.43 34.80 330.33 124 120 600 0.20 200 0.60 3.0 19G 50.2533.08 325.61 188 120 600 0.19 200 0.59 3.0 19H 50.15 34.87 318.17 58 120600 0.21 200 0.66 3.0 19I 55.02 34.02 323.59 53 120 600 0.44 200 0.743.0 19J 7.46 9.04 50.6 47 120 150 0.22 76.7 0.36 0.5 DEZ Cocat 1 Cocat 1Cocat 2 Cocat 2 Zn⁴ in Poly Flow Conc. Flow Conc. Flow polymer Rate⁵Conv⁶ Polymer Ex. lb/hr ppm lb/hr ppm lb/hr ppm lb/hr wt % wt % Eff.⁷19A 0.70 4500 0.65 525 0.33 248 83.94 88.0 17.28 297 19B 0.24 4500 0.63525 0.11  90 80.72 88.1 17.2 295 19C 0.69 4500 0.61 525 0.33 246 84.1388.9 17.16 293 19D 1.39 4500 0.66 525 0.66 491 82.56 88.1 17.07 280 19E1.04 4500 0.64 525 0.49 368 84.11 88.4 17.43 288 19F 0.74 4500 0.52 5250.35 257 85.31 87.5 17.09 319 19G 0.54 4500 0.51 525 0.16 194 83.72 87.517.34 333 19H 0.70 4500 0.52 525 0.70 259 83.21 88.0 17.46 312 19I 1.724500 0.70 525 1.65 600 86.63 88.0 17.6 275 19J 0.19 — — — — — — — — —¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdimethyl ⁴ppm in final product calculated by mass balance ⁵polymerproduction rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 9A Polymer Physical Properties Heat of Tm − CRYSTAF Density Mw MnFusion Tm Tc TCRYSTAF TCRYSTAF Peak Area Ex. (g/cc) I2 I10 I10/I2(g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.) (wt%) 19A 0.87810.9 6.4 6.9 123700 61000 2.0 56 119 97 46 73 40 19B 0.8749 0.9 7.3 7.8133000 44300 3.0 52 122 100 30 92 76 19C 0.8753 5.6 38.5 6.9 81700 373002.2 46 122 100 30 92  8 19D 0.8770 4.7 31.5 6.7 80700 39700 2.0 52 11997 48 72  5 19E 0.8750 4.9 33.5 6.8 81800 41700 2.0 49 121 97 36 84 1219F 0.8652 1.1 7.5 6.8 124900 60700 2.1 27 119 88 30 89 89 19G 0.86490.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19H 0.8654 1.0 7.0 7.1131600 66900 2.0 26 118 88 — — — 19I 0.8774 11.2 75.2 6.7 66400 337002.0 49 119 99 40 79 13 19J 0.8995 5.6 39.4 7.0 75500 29900 2.5 101 122106 — — —

TABLE 9B Polymer Physical Properties of Compression Molded FilmImmediate Set Immediate Set Immediate Set Recovery Recovery RecoveryDensity Melt Index after 100% Strain after 300% Strain after 500% Strainafter 100% after 300% after 500% Example (g/cm³) (g/10 min) (%) (%) (%)(%) (%) (%) 19A 0.878 0.9 15 63 131  85 79 74 19B 0.877 0.88 14 49 97 8684 81 19F 0.865 1 — — 70 — 87 86 19G 0.865 0.9 — — 66 — — 87 19H 0.8650.92 — 39 — — 87 —

TABLE 9C Average Block Index For exemplary polymers¹ Example Zn/C₂ ²Average B1 Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3.15 0.59¹Additional information regarding the calculation of the block indicesfor various polymers is disclosed in U.S. Patent Application Serial No.11/376,835, entitled “Ethylene/a-Olefin Block Interpolymers”, filed onMar. 15, 2006, in the name of Colin L. P. Shan, Lonnie Hazlitt. et. al.and assigned to Dow Global Technologies Inc., the disclose of which isincorporated by reference herein in its entirely. ²Zn/C₂ * 1000 = (Znfeed flow * Zn concentration/1000000/Mw of Zn)/(Total Ethylene feedflow * (1-fractional ethylene conversion rate)/Mw of Ethylene) * 1000.Please note that “Zn” in “Zn/C₂ * 1000” refers to the amount of zinc indiethyl zine (“DEZ”) used in the polymerization process. and “C2” refersto the amount of ethylene used in the polymerization process.

Examples 20 and 21

The ethylene/α-olefin interpolymer of Examples 20 and 21 were made in asubstantially similar manner as Examples 19A-I above with thepolymerization conditions shown in Table 11 below. The polymersexhibited the properties shown in Table 10. Table 10 also shows anyadditives to the polymer.

TABLE 10 Properties and Additives of Examples 20-21 Example 20 Example21 Density (g/cc) 0.8800 0.8800 MI 1.3 1.3 Additives DI Water 100 DIWater 75 Irgafos 168 1000 Irgafos 168 1000 Irganox 1076 250 Irganox 1076250 Irganox 1010 200 Irganox 1010 200 Chimmasorb 100 Chimmasorb 80 20202020 Hard segment split 35% 35% (wt %)

Irganox 1010 isTetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane.Irganox 1076 isOctadecyl-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate. Irgafos 168is Tris(2,4-di-t-butylphenyl)phosphite. Chimasorb 2020 is1,6-Hexanediamine, N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymerwith 2,3,6-trichloro-1,3,5-triazine, reaction products with,N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

TABLE 11 Polymerization Conditions for Examples 20-21 Cat A1² Cat A1 CatB2³ Cat B2 DEZ DEZ C₂H₄ C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc FlowEx. lb/hr lb/hr lb/hr sccm¹ ° C. ppm lb/hr ppm lb/hr wt % lb/hr 20 130.7196.17 712.68 1767 120 499.98 1.06 298.89 0.57 4.809423 0.48 21 132.13199.22 708.23 1572 120 462.4 1.71 298.89 0.6 4.999847 0.47 Cocat 1 Cocat1 Cocat 2 Cocat 2 Zn⁴ in Poly Conc. Flow Conc. Flow polymer Rate⁵ Conv⁶Polymer Ex. ppm lb/hr ppm lb/hr ppm lb/hr wt % wt % Eff.⁷ 20 5634.361.24 402.45 0.478 131 177 89.25 16.94 252.04 21 5706.4 1.61 289.14 1.36129 183 89.23 17.52 188.11 * Comparative, not an example of theinvention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl ⁴ppm Zinc in final product calculated by mass balance⁵polymer production rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g ZMeasurements for Examples 22-33

By the term “MI,” is meant melt index, I₂, in g/10 min, measured usingASTM D-1238-04, Condition 190° C./2.16 kg for polyethylene-basedpolymers (Condition 230° C./2.16 kg for polypropylene-based polymers).

Differential Scanning Calorimetry (DSC) can be used to measurecrystallinity in polyethylene (PE) based samples and polypropylene (PP)based samples. A sample is pressed into a thin film at a temperature of190° C. About five to eight mg of film sample is weighed and placed in aDSC pan. The lid is crimped on the pan to ensure a closed atmosphere.The sample pan is placed in a DSC cell, and then heated, at a rate ofapproximately 10° C./min, to a temperature of 180° C. for PE (230° C.for PP). The sample is kept at this temperature for three minutes. Thenthe sample is cooled at a rate of 10° C./min to −60° C. for PE (−40° C.for PP), and kept isothermally at that temperature for three minutes.The sample is next heated at a rate of 10° C./min until complete melting(second heat). The percent crystallinity is calculated by dividing theheat of fusion (H_(f)), determined from the second heat curve, by atheoretical heat of fusion of 292 J/g for PE (165 J/g, for PP), andmultiplying this quantity by 100 (for example, % cryst.=(H_(f)/292J/g)×100 (for PE)).

Unless otherwise stated, melting point(s) (T_(m)) of each polymer sampleis determined from the second heat curve obtained from DSC, as describedabove. The crystallization temperature (T_(c)) is measured from thefirst cooling curve.

Density is measured in accordance with ASTM D-792-00.

Fourier Transform Infrared Spectroscopy (FTIR) Analysis

Maleic Anhydride Content

The concentration of maleic anhydride is determined by the ratio of peakheights of the maleic anhydride at wave number 1791 cm⁻¹ to the polymerreference peak, which in case of polyethylene, is at wave number 2019cm⁻¹. Maleic anhydride content is calculated by multiplying this ratiowith the appropriate calibration constant. The equation used for maleicgrafted olefin multiblock interpolymers has the following form.MAH(wt. %)=A*{[FTIR PeakArea@1791 cm⁻¹]/[FTIR PeakArea 2019 cm⁻¹]+B*[FTIR PeakArea@1712 cm⁻¹]/[FTIR_PeakArea@2019 cm⁻¹]}  (Eqn. 1)

The calibration constant A can be determined using C13 NMR standards.The actual calibration constant may differ slightly depending on theinstrument and polymer. The second component at wave number 1712 cm⁻¹accounts for the presence of maleic acid, which is negligible forfreshly grafted material. Over time however, maleic anhydride is readilyconverted to maleic acid in the presence of moisture. Depending onsurface area, significant hydrolysis can occur in just a few days underambient conditions. The acid has a distinct peak at wave number 1712cm⁻¹. The constant B in Equation 1 is a correction for the difference inextinction coefficients between the anhydride and acid groups.

The sample preparation procedure begins by making a pressing, typically0.05 to 0.15 millimeters in thickness, in a heated press, between twoprotective films, at 150-180° C. for 1 hour. Mylar and Teflon aresuitable protective films to protect the sample from the platens.Aluminum foil must never be used (maleic anhydride reacts withaluminum). Platens should be under pressure (˜10 ton) for about 5minutes. The sample is allowed to cool to room temperature, placed in anappropriate sample holder, and then scanned in the FTIR. A backgroundscan should be run before each sample scan or as needed. The precisionof the test is good with an inherent variability of less than ±5%.Samples should be stored with desiccant to prevent excessive hydrolysis.Moisture content in the product has been measured as high as 0.1 weightpercent. The conversion of anhydride to acid however is reversible withtemperature but may take up to one week for complete version. Thereversion is best performed in a vacuum oven at 150° C. a good vacuum(near 30 inches Hg) is required. If the vacuum is less than adequate thesample tends to oxidize resulting in an infrared peak at approximately1740 cm⁻¹ which will cause the values to below. Maleic anhydride andacid are represented by peaks at about 1791 and 1712 cm¹, respectively.

Examples 22-33

The following examples illustrate, but do not, either explicitly or byimplication, limit the present invention.

The following polymers were used in the examples below.

EN82 (Engage™ 8200) is a random ethylene/octene-1 copolymer, with adensity of 0.870 and a melt index (I2) of 5.

EN84 (Engage™ 8400) is a random ethylene/octene-1 copolymer, with adensity of 0.870 and a melt index (I2) of 30.

EN81 (Engage™ 8100) is a random ethylene/octene-1 copolymer, with adensity of 0.870 and a melt index (I2) of 1.

EN83 (Engage™ 8130) is a random ethylene/octene-1 copolymer, with adensity of 0.864 and a melt index (I2) of 13.

AM21 (Amplify™ GR-216) is a random ethylene/octene-1 copolymer graftedwith ca. (about) 0.8 wt % maleic anhydride, with a density of 0.875 anda melt index (I2) of 1.3.

PU80 (Pellethane™ 2102-80A) is a thermoplastic polyurethane, with adensity of 1.18 and a melt index (I2) of 4 measured at 190° C. and 8.7Kg.

Example 22

A poly(ethylene-co-octene) copolymer grafted with 0.80 wt % maleicanhydride (45 grams, AMPLIFY™ GR-216) was added to the bowl of a Haakemixer, set at 160° C., and the polymer was allowed to melt and flux fortwo minutes. To the molten polymer as added 1.61 g (18.2 mmol; 5 equiv.)of N-ethyl-ethylenediamine in dropwise fashion. After the diamineaddition, the polymer melt was allowed to mix for an additional fiveminutes, before being removed from the Haake mixer, and allowed to cool.Infrared analysis of the resulting product indicated essentiallycomplete conversion of the grafted anhydride functionality (1790 cm⁻¹)to imide functionality (1710 cm⁻¹).

Comparative Example 22A

The procedure in Example 1 was repeated, only 1.35 g ofN-methyl-ethylenediamine was used in place of N-ethyl-ethylenediamine.The melt reaction product crosslinked upon addition of this diamine,affording an insoluble gel.

Comparative Example 22B

The procedure in Example 1 was repeated, only 2.35 g (18.2 mmol) ofN-(2-aminoethyl)-piperazine was used in place ofN-ethyl-ethylenediamine. The melt reaction product crosslinked uponaddition of this diamine, affording an insoluble gel.

Example 23

The procedure detailed in Example 22 was repeated, only 1.11 g (18.2mmol) if ethanolamine was substituted for the diamine. The resultingproduct likewise showed complete conversion from anhydride functionalityto N-(2-hydroxyethyl)maleimide by infrared analysis.

Example 24 Preparation of Maleamic Acid

Maleic anhydride (7.84 g (80 mmol) was dissolved in 20 mL of acetone. Tothe maleic anhydride solution was added another solution of ethanolamine(4.88 g, 80 mmol) dissolved in 10 mL of acetone. The reaction solutionwas kept cool using an ice bath, and after all the ethanolamine solutionwas added, the solution was stripped on a rotary evaporator to afford alight yellow oil, which crystallized upon standing. Proton NMR analysisof the crystalline material was consistent with that of the desiredmaleamic acid product, as shown below in structure (II):

Example 25

Poly(ethylene-co-octene) copolymer (45 g, ENGAGE™ 8400) was added to aHaake mixer set at a temperature of 170° C., and allowed to melt andflux for two minutes. To the molten polymer was added 1.0 g of maleicanhydride, and the mixture was fluxed for another two minutes, and then0.10 wt % of Luperox™ 101 peroxide (90% active) was added. After anadditional five minutes of reaction time, 1.21 g (19.8 mmol) ofethanolamine was added and the reaction allowed to continue for fivemore minutes. The mixer was stopped, and the functionalized polymer wasremoved and allowed to cool. A portion of the reaction product wasdissolved in hot toluene and precipitated into cold methanol to removeunreacted reagents and byproducts. Infrared analysis of the precipitatedpolymer indicated that the ethylene-octene copolymer was indeedfunctionalized with N-(2-hydroxy)-maleimide. The product appearedidentical to that prepared in Examples 2 and 3 based on its infraredspectrum.

Example 26

The same procedure as described in Example 25 was repeated, only 1.63 g(18.5 mmol) of N-ethyl-ethylenediamine was used in place ofethanolamine. Again, infrared analysis of the resulting polymer afterprecipitation was consistent with functionalization of theethylene-octene elastomer with N—(N-ethylaminoethyl)-maleimide. Theproduct appeared identical to that prepared in Example 1 based on itsinfrared spectrum.

Example 26 Adhesion Comparison

Samples of the polymers prepared in Examples 22 and 23 were compressionmolded into ⅛ inch thick plaques, along with the maleic anhydridestarting polymer (AMPLIFY™ GR-216), an unfunctionalized control (ENGAGE™8100), and a thermoplastic polyurethane (TPU; PELLETHANE™ 2102-80A).Bars, “½ inch” in width, were cut from the plaques, and were compressionmolded to bars of the TPU at 180° C. for two minutes. The level ofadhesion between the TPU and the various polyolefins was accessed as“cohesive failure” or “adhesive failure” based on the following criteriawhen pulling them apart:

Cohesive failure: one or both of the polymers deforms and/or breaksbefore the interface between them fails.

Adhesive failure: the interface between the polymers fails first.

The samples involving TPU molded to unfunctionalized polyolefin (ENGAGE™8100), maleic anhydride grafted polyolefin (AMPLIFY™ GR-216), andhydroxy-functionalized polyolefin (Example 23) all failed adhesively.The sample involving TPU molded to amino-functionalized polyolefinfailed cohesively.

Summary of Results—Direct Addition Process

Table 12 summarizes the results of various experiments to react 0.80 wt% maleic anhydride grafted ethylene-octene elastomer with a number ofprimary-secondary diamines. The diamines were added to the polymer melt.A crosslinked polymer formed when N-(methyl)ethylenediamine orN-(2-aminoethyl)piperazine was used as the diamine.

TABLE 12 diamine imidization product *

x-linked

x-linked

x-linked

soluble

soluble

Example 28 Preparation of Hydroxy-Functional Elastomer by SuccessiveMaleation and Imidization

A sample of ethylene-octene elastomer (45 g, ENGAGE 8130) was mixed in aHaake melt blender for two minutes at 170° C. and 100 rpm. To this wasadded maleic anhydride (1.0 g, 10.2 mmol), and the resulting mixture wasblended for an additional two minutes, before the addition of 0.0504grams of active Luperox™ 101 peroxide (0.7 mmol RO.). After anadditional five minutes of mixing time at 170° C., to allow grafting ofthe maleic anhydride to the elastomer, 1.2 grams of ethanolamine (19.7mmol) was added, and the resulting mixture was allowed to react for anadditional two minutes at 170° C., to convert maleic anhydride tohydroxy functionality. The product was removed from the Haake blenderand allowed to cool.

A sample of the product was dissolved in hot toluene, and precipitatedby addition to an excess of cold methanol, in order to remove unreactedmaleic anhydride, ethanolamine, and any residual peroxide and/or itsdecomposition products. The precipitated sample was redissolved in hottoluene, and reprecipitated into excess methanol, a second time, tofurther purify the sample for analysis. A portion of the twiceprecipitated sample was dissolved in warm deuterated1,1,2,2-tetrachloroethane (˜30 mg polymer/2 mL solvent), and analyzed byproton NMR (300 MHz; 80° C.). The characteristic chemical shifts for thefour hydrogens of the 2-hydroxyethylimide group were observed at 3.7-3.8ppm, and the relative area of the peak was 0.81% compared to the totalarea (hydroxyethylimide+ethylene-octene signal areas).

Example 29 Preparation of Hydroxy-Functional Elastomer by DirectGrafting of Maleamic Acid

A sample of ethylene-octene elastomer (45 g, ENGAGE 8130) was mixed in aHaake melt blender for two minutes at 170° C. and 100 rpm. To this wasadded 1.5 gram of maleamic acid (9.4 mmol; prepared per EXAMPLE 24), andthe resulting mixture was blended for an additional two minutes, beforethe addition of 0.0504 grams of active Luperox™ 101 peroxide (0.7 mmolRO.). After an additional five minutes of mixing time to 170° C., toallow grafting of the maleamic acid to the elastomer, the product wasremoved from the Haake blender and allowed to cool. A sample of theproduct was dissolved in hot toluene and precipitated into an excess ofcold methanol in order to remove unreacted maleamic acid and residualperoxide and/or its decomposition products.

The precipitated sample was redissolved in holt toluene andreprecipitated into methanol, a second time, to further purify thesample for analysis. A portion of the twice precipitated sample wasdissolved in warm, deuterated 1,1,2,2-tetrachloroethane (˜30 mgpolymer/2 mL solvent), and analyzed by proton NMR (300 MHz; 80° C.). Thecharacteristic chemical shifts for the four hydrogens of the2-hydroxyethylimide group were observed at 3.7-3.8 ppm, and relativearea of the peak was 1.73% compared to the total area(hydroxethylimide+ethylene-octene signal areas). These data suggest thatmore hydroxyethylmaleimide functionality was grafted onto the elastomerbackbone by the procedure in Example 29 versus that described in Example28.

Example 30 Preparation of Amine-Functionalized Ethylene-Octene Elastomervia Diamine Imbibe Process

Poly(ethylene-co-octene) copolymer (45 grams) grated with 0.74 wt %maleic anhydride (3.4 mmol anhydride) was placed in a sealed containerwith 0.60 grams of N-ethylethylenediamine (6.8 mmol) and allowed tostand for 4 hours, allowing the diamine to completely imbibe into thepellets of the MAH grafted copolymer. The pellets were then added to thebowl of a Haake mixer set at 180° C., and the polymer was allowed tomelt and mix at that temperature for five minutes. The product was thenremoved from the Haake mixer, and allowed to cool to room temperature.Infrared analysis of the resulting product indicated essentiallycomplete conversion of the grafted anhydride functionality (1790 cm⁻¹)to imide functionality (1710 cm⁻¹) in accordance with the followingchemical equation:

In addition, a small compression molded film of the (ethylene-co-octene)copolymer, grafted with maleic anhydride, was characterized by FTIR, andthen the film was placed in a small vial at room temperature, along witha molar excess of N-(ethyl)ethylene diamine compared to the maleicanhydride grafted to the ethylene-octene copolymer. After a period ofseveral hours, the now-imbibed film was again characterized by FTIR, andthe spectrum indicated essentially complete conversion of the originalmaleic anhydride groups (1790 cm⁻¹) to maleamic acid groups (1640 cm⁻¹)consistent with the following chemical equation:

These data suggest that partial reaction occurs between maleic anhydrideand the diamine at room temperature, before the material is subjected toelevated temperature melt mixing. This process is advantaged in that noseparate diamine feed system or process control needs to be added to themelt mixing equipment used to prepare these functionalized polymers.

Example 31

The procedure in Example 30 was repeated, only 0.50 g ofN-methyl-ethylenediamine was used in place of N-ethyl-ethylenediamine.The reaction product was completely soluble and not crosslinked. This isin contrast to the direct addition method of Comparative Example 22A,which yielded a crosslinked product.

Example 32

The procedure in Example 30 was repeated, only 0.88 g ofN-(2-aminoethyl)-piperazine was used in place ofN-ethyl-ethylenediamine. The reaction product was completely soluble andnot crosslinked. This is in contrast to the direct addition method ofComparative Example 22B, which yielded a crosslinked product.

Summary of Results—Imbibe Process

Table 13 summarizes the results of the imbibing examples. As shown inTable 13, all of the diamines produced soluble polymer product.Primary-primary diamines typically produced crosslinked polymer.

TABLE 13 diamine imidization

soluble

soluble

soluble

soluble

solubleMorphology Study I

Samples of amine- and hydroxyl-functionalized ethylene-octene elastomerprepared according to Examples 22 and 23, respectively, were blendedwith a thermoplastic polyurethane polymer (TPU; PELLETHANE™ 2102-80A).The following controls were each blended with the TPU; unfunctionalizedethylene-octene elastomer (ENGAGE™ 8100) and maleicanhydride-functionalized ethylene-octene elastomer (AMPLIFY GR-216). Themass ratio of TPU to ethylene-octene polymer in the blends was 80/20,and the blends were prepared by mixing both polymeric components at 180°C., for five minutes, in a Haake blender. The resulting blendmorphologies were examined using transmission electron microscopy, andare shown in FIG. 8.

The data clearly show that the functionality in the ethylene-octenephase improved the dispersion of the ethylene-octene polymer in the TPUphase, as compared to the unfunctionalized controls (ENGAGE™ 8100). Inparticular, it is advantageous to employ amine functionality to achievethe best dispersion of ethylene-octene copolymer in TPU.

The mean particles sizes, as determined from the micrographs, were asfollows:

1) 80/20 TPU/ENGAGE mean size=0.84±0.79 μm (bimodal),

2) 80/20 TPU/ENGAGE-g-MAH mean size=0.35±0.28 μm,

3) 80/20 TPU/ENGAGE-g-hydroxyl mean size=0.42±0.32 μm, and

4) 80/20 TPU/ENGAGE-g-amine mean size=0.11±0.10 μm.

The smaller particle sizes may be due to better interfacial associationsand/or compatibility between the functionalized olefin multiblockinterpolymers and the polyurethane. The amine functionalization and thehydroxyl functionalization can each react with urethane groups along thebackbone of the polyurethane.

Morphology Study II

An amine-functionalized ethylene-octene elastomer, prepared according tothe procedure described in Example 25, was blended with unfunctionalizedethylene-octene elastomer at various ratios. The unfunctionalizedelastomer was ENGAGE™ 8100 with a density of 0.87 g/cc and a melt indexof 1.0 g/10 min (190° C./2.16 Kg). The blending was carried out in aHaake melt mixer at a temperature of about 180° C. for five minutes. Theblends had the following compositions on a relative weight basis.

Blend 1: 50 wt % amino-functionalized elastomer+50 wt % ENGAGE™ 8100

Blend 2: 25 wt % amino-functionalized elastomer+75 wt % ENGAGE™ 8100

Blend 3: 12 wt % amino-functionalized elastomer+88 wt % ENGAGE™ 8100

Subsequently, these blends were then compounded with a thermoplasticpolyurethane (TPU), namely PELLETHANE™ 2102-80A with a density of 1.18g/cc and a melt index of 4.0 g/10 min (190° C./8.7 kg). The relativeweight ratio of the amino-functionalized elastomer, or its blend withunfunctionalized elastomer, to that of the TPU was 20/80. In addition,two control samples were prepared in a similar manner. Control A was ablend of 80 wt % TPU with 20 wt % ENGAGE™ 8100 (0% amino-functionalizedresin) and Control B was a blend of 80 wt % TPU with theamino-functionalized elastomer itself (100% amino-functionalized resin).

The compounding was carried out in a Haake mixer at temperature of about180° C. for five minutes. Upon cooling, a small portion of theTPU/polyolefin elastomer blend was compression molded into a smallplaque, and then the morphology of the blend was assessed using standardtransmission electron microscopy techniques. The results are illustratedin FIG. 9.

These results indicate that the functionalized ethylene-octene elastomercan be diluted with unfunctionalized resin, and still give rise to asignificant improvement in compatibility when blended with a polarpolymer, such as TPU. In FIG. 9, the weight percent amino-functionalizedelastomer in polyolefin (dispersed) phase is as follows: Control A—0 wt%, Blend 3—12 wt %, Blend 2—25 wt %, Blend 1—50 wt %, Control B—100 wt%.

Adhesion to Polycarbonate

Polycarbonate Substrate

Dow's Calibre™ 200-22 polycarbonate pellets were injection-moldedagainst a textured plaque to obtain polycarbonate plaques with identicaltextured surfaces, and designated as CPM501. This textured feature iscommon in the over molding industry because it provide some interlockingof the different layers.

Functionalized Engage™ Material

Three imidized Engage™ material compounds, a maleic anhydride (MAH)Engage™, a primary-hydroxy functionalized Engage™, and secondary aminefunctionalized Engage™ were used in this study. A schematic of eachfunctional group is shown below.

Fabrication of the Peel Test Specimen

The functionalized Engage™ materials were first pressed into thin films,less than “ 1/32 inch” width, using a threefold cycle of compression of284° F., using consecutive pressures of 1,000 psi, then 40,000 psi, andthen 40,000 psi, respectively, for the following dwell times: threeminutes, three minutes and seven minutes, respectively.

Each film of functionalized Engage™ material was welded against a “⅛inch” piece of regular Engage™ material using a protocol identical tothe one described in the previous paragraph. A threefold cycle ofcompression at 284° F., using consecutive pressures of 1,000 psi, then40,000 psi, and then 40,000 psi, respectively, for the following dwelltimes: three minutes, three minutes and seven minutes, respectively.

The assemble functionalized Engage™/Engage™ was then pressed against thetextured polycarbonate plaque. Mylar was inserted at the edge of theplaque to create a zone with no adhesion between the functionalizedEngage™ material and the polycarbonate surface. The functionalizedEngage™ face was pressed against the textured polycarbonate using athreefold cycle of compression at 284° F. with consecutive pressures of1,000 psi, then 40,000 psi, and then 40,000 psi, respectively, for nineseconds, one minute and seven minutes dwell times, respectively. Thethickness of the Engage™ material was between 1.5 and 1.6 millimeter.

Specimens were cooled to ambient temperature. The final step of thepreparation was to stamp the Engage™/functionalized Engage™ with a oneslit die to create 6 to 8 long stripes, parallel to one edge of theplaque, of about 5.2 mm width and 50 mm long. A schematic of this peeltest specimen is shown in FIG. 10.

Peel Test Measurements

The free end of the functionalized (Engage™)/Engage™) stripe was pulledusing an air grip device on a 4201 Instron tensile tester machine at 23°C. and 50% RH (relative humidity). The polycarbonate plaque was tightlyattached to an Instron peel test device, moving at the same speed as thecross-head, but in a perpendicular direction, in such a way that thepull force was always applied perpendicularly to the plaque. Thisspecific setup is called a 90 degree peel test, referenced in ASTMD6862-04, entitled “Standard Test Method for 90 Degree Peel Resistanceof Adhesives.” A schematic of the test set-up is shown in FIG. 11.

The speed of the displacement was constant at 0.3 millimeter per second.Force and displacement were recorded automatically through Bluehill™software from Instron. The load, reported in kilogram or Newton (1kg=9.81 Newton), was then divided by the width of the stripe to obtainthe peel strength in Newton per millimeter. The median value and thestandard deviation of the peel strength over a range of 10 to 30millimeters are reported in Table 14 below.

TABLE 14 Peel Strength versus Functionalized Engage SecondaryFunctionalization Maleic anhydride Primary hydroxyl amine MEDIAN 0.2560.543 1.034 STDEV 0.028 0.029 0.062

Representative peel strength profiles for the three imidized Engage™material compounds, the maleic anhydride (MAH) Engage™, theprimary-hydroxy functionalized Engage™, and the secondary aminefunctionalized Engage™, are shown in FIGS. 12-14, respectively.

Example 33

The procedures in Examples 22-32 may be repeated except that the randomethylene/octene-1-copolymer may be substituted with an ethylene/α-olefininterpolymer characterized by one or more of the followingcharacteristics:

(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², or

(b) has a Mw/Mn from about 1.7 to about 3.5, and is characterized by aheat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsiusdefined as the temperature difference between the tallest DSC peak andthe tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH havethe following relationships:

ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,

ΔT≧48° C. for ΔH greater than 130 J/g.

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(c) is characterized by an elastic recovery, Re, in percent at 300percent strain and 1 cycle measured with a compression-molded film ofthe ethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when the ethylene/α-olefin interpolymer issubstantially free of a cross-lined phase:Re>1481−1629(d); or

(d) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has amolar comonomer content of at least 5 percent higher than that of acomparable random ethylene interpolymer fraction eluting between thesame temperatures, wherein said comparable random ethylene interpolymerhas the same comonomer(s) and a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(e) is characterized by a storage modulus at 25° C., G′(25° C.), and astorage modulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.)to G′(100° C.) is from about 1:1 to about 10:1; or

(f) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1 and a molecular weightdistribution, Mw/Mn, greater than about 1.3 or

(g) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3. Suchethylene/α-olefin interpolymers may be described in, for example,Examples 1-21 above.

Example 34

This is an example of using a one-step grafting process to introducehydroxy functionality to an olefin block copolymer backbone. 45.2 gramsof OBC 9500 olefin block copolymer (an ethylene/octene-1 multiblockcopolymer, with a density of 0.877 g/cc and a melt index (I2) of 5 g/10min and a product of The Dow Chemical Company) was introduced into themixing bowl of a Haake batch melt mixer set at a temperature of 180° C.and a mixing rotor speed of 100 rpm. After melting and fluxing the OBCfor 2 minutes, 1.0 grams of N-(2-hydroxyethyl)-maleamic acid was addedand allowed to mix with the polyolefin for ca. 15 seconds before 0.051grams of Luperox™ 101 peroxide was also added. The subsequent mixturewas allowed to react for 5 minutes at ca. 180° C. before the mixer wasstopped and the reaction product removed and allowed to cool to roomtemperature. A 2 gram portion of the product was dissolved in hottoluene and then precipitated by pouring the toluene solution into anexcess of cold methanol. The product was filtered and dried in vacuoovernight at 60° C. Subsequently, the precipitated product was analyzedby both fourier transform infrared spectroscopy (FTIR) and nuclearmagnetic resonance spectroscopy (NMR). The FTIR spectrum of the purifiedproduct showed a new absorbance at 1700-1705 cm⁻¹characteristic of imidecarbonyl groups, as well as an absorbance at 3450 cm⁻¹ associated withthe hydroxyl group. Analysis of the purified product by NMR showed a newpeak at ˜3.8 ppm, characteristic of the four protons of the2-hydroxyethyl moiety.

Comparative Example

This is an example of using a two-step grafting process to introducehydroxy functionality to an olefin block copolymer backbone. 45.0 gramsof OBC 9500-graft-maleic anhydride (1.2 wt % anhydride) olefin blockcopolymer (OBC) was introduced into the mixing bowl of a Haake batchmelt mixer set at a temperature of 180° C. and a mixing rotor speed of100 rpm. After melting and fluxing the OBC-g-MAH for 2 minutes, 1.1grams of monoethanolamine was added and allowed to mix with thepolyolefin or 5 minutes at ca. 180° C. before the mixer was stopped andthe reaction product removed and allowed to cool to room temperature. A2 gram portion of the product was dissolved in hot toluene and thenprecipitated by pouring the toluene solution into an excess of coldmethanol. The product was filtered and dried in vacuo overnight at 60°C. Subsequently, the precipitated product was analyzed by both fouriertransform infrared spectroscopy (FTIR) and nuclear magnetic resonancespectroscopy (NMR). The FTIR spectrum of the purified product showed anabsorbance shift from 1790 cm−1 to 1700-1705 cm⁻¹ characteristic ofconversion of the anhydride groups to imide groups, as well as anabsorbance at 3450 cm⁻¹ associated with the hydroxyl group. Analysis ofthe purified product by NMR likewise showed a new peak at ˜3.8 ppm,characteristic of the four protons of the 2-hydroxyethyl moiety.

Example 35

This is an example of using a one-step grafting process to introducehydroxy functionality to an olefin block copolymer backbone. 45.0 gramsof OBC 9807.10 olefin block copolymer (an ethylene/octene-1 multiblockcopolymer, with a density of 0.877 g/cc and a melt index (I2) of 15 g/10min and a product of The Dow Chemical Company) was introduced into themixing bowl of a Haake batch melt mixer set at a temperature of 180° C.and a mixing rotor speed of 100 rpm. After melting and fluxing the OBCfor 2 minutes, 1.0 grams of N-(2-hydroxyethyl)-maleamic acid was addedand allowed to mix with the polyolefin for ca. 15 seconds before 0.051grams of Luperox™ 101 peroxide was also added. The subsequent mixturewas allowed to react for 5 minutes at ca. 180° C. before the mixer wasstopped and the reaction product removed and allowed to cool to roomtemperature. A 2 gram portion of the product was dissolved in hottoluene and then precipitated by pouring the toluene solution into anexcess of cold methanol. The product was filtered and dried in vacuoovernight at 60° C. Subsequently, the precipitated product was analyzedby both fourier transform infrared spectroscopy (FTIR) and nuclearmagnetic resonance spectroscopy (NMR). The FTIR spectrum of the purifiedproduct showed a new absorbance at 1700-1705 cm⁻¹ characteristic ofimide carbonyl groups, as well as an absorbance at 3450 cm⁻¹ associatedwith the hydroxyl group. Analysis of the purified product by NMR showeda new, strong peak at ˜3.8 ppm, characteristic of the four protons ofthe 2-hydroxyethyl moiety.

Comparative Example

This is an example of using the two-step grafting process to introducehydroxy functionality to an olefin block copolymer backbone. 45.0 gramsof OBC 9807.01-graft-maleic anhydride (1.1 wt % anhydride) olefin blockcopolymer (OBC) was introduced into the mixing bowl of a Haake batchmelt mixer set at a temperature of 180° C. and a mixing rotor speed of100 rpm. After melting and fluxing the OBC-g-MAH for 2 minutes, 1.2grams of monoethanolamine was added and allowed to mix with thepolyolefin for 5 minutes at ca. 180° C. before the mixer was stopped andthe reaction product removed and allowed to cool to room temperature. A2 gram portion of the product was dissolved in hot toluene and thenprecipitated by pouring the toluene solution into an excess of coldmethanol. The product was filtered and dried in vacuo overnight at 60°C. Subsequently, the precipitated product was analyzed by both fouriertransform infrared spectroscopy (FTIR) and nuclear magnetic resonancespectroscopy (NMR). The FTIR spectrum of the purified product showed anabsorbance shift from 1790 cm−1 to 1700-1705 cm⁻¹ characteristic ofconversion of the anhydride groups to imide groups, as well as anabsorbance at 3450 cm⁻¹ associated with the hydroxyl group. Analysis ofthe purified product by NMR likewise showed a new, strong peak at ˜3.8ppm, characteristic of the protons of the four protons of the2-hydroxyethyl moiety.

We claim:
 1. A process for preparing a functionalized olefin multiblockinterpolymer, said process comprising: A) grafting onto the backbone ofan olefin multiblock interpolymer at least one compound comprising atleast one “amine-reactive” group to form a grafted olefin multiblockinterpolymer; B) reacting a primary-secondary diamine with the graftedolefin multiblock interpolymer; and wherein step B) takes placesubsequent to step A), without the isolation of the grafted olefinmultiblock interpolymer, and wherein both steps A) and B) take place ina melt reaction; and wherein said olefin multiblock interpolymercomprises an ethylene/α-olefin multiblock interpolymer characterized byone or more of the following characteristics prior to functionalization:(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², or (b) has a Mw/Mn from about 1.7to about 3.5, and is characterized by a heat of fusion, ΔH in J/g, and adelta quantity, ΔT, in degrees Celsius defined as the temperaturedifference between the tallest DSC peak and the tallest CRYSTAF peak,wherein the numerical values of ΔT and ΔH have the followingrelationships: ΔT>−0.1299 (ΔH)+62.81 for ΔH greater than zero and up to130 J/g, ΔT≧48° C. for ΔH greater than 130 J/g, wherein the CRYSTAF peakis determined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.; or (c) is characterized by anelastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenthe ethylene/α-olefin interpolymer is substantially free of across-linked phase: Re>1481-1629(d); or (d) has a molecular fractionwhich elutes between 40° C. and 130° C. when fractionated using TREF,characterized in that the fraction has a molar comonomer content of atleast 5 percent higher than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, whereinsaid comparable random ethylene interpolymer has the same comonomer(s)and a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the ethylene/a-olefininterpolymer; or (e) is characterized by a storage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C., G′(100° C.), wherein theratio of G′(25° C.) to G′(100° C.) is from about 1:1 to about 10:1; or(f) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1 and a molecular weightdistribution, Mw/Mn, greater than about 1.3 or (g) an average blockindex greater than zero and up to about 1.0 and a molecular weightdistribution, Mw/Mn, greater than about 1.3.
 2. The process of claim 1,wherein the primary-secondary diamine is selected from the groupconsisting N-ethylethylenediamine, N-phenylethylenediamine,N-phenyl-1,2-phenylene-diamine, N-phenyl-1,4-phenylenediamine, andN-(2-hydroxyethyl)-ethylenediamine.
 3. The product of the process ofclaim
 1. 4. An article comprising at least one component formed from theproduct of claim 3.